BK9780851862514 00001

1
Photoelectron Spectroscopy
BY A. HAMNETT AND A. F. ORCHARD
There has been intense activity in the general field of photoelectron (p.e.)spectroscopy, especiallyas regards the low-energy aspect of the technique which normally involves photoionisation in the vapour phase using U.V.radiation sources. A very important book on u.v.-p.e. spectroscopy by Turner et a!. has appeared, the fruit of many years research by the pioneering Imperial CollegeOxford group. P.e. spectroscopy using X-ray sources2 (X-p.e. spectroscopy or ESCA*) has in the past been almost entirely confined to the solid state, but in late 1969 an authoritative monograph by Siegbahn et ~ 1 on the X-p.e. spectroscopy of . ~ gases was published. The proceedings of a Royal Society discussion on p.e. spectroscopy held in February 1969 has now appeared in print :4 this provides a most interesting variety of articles on both u.v.-p.e. and X-p.e. studies. A very useful recent review by Brundle should also be mentioned. We report on u.v.-p.e. and X-p.e. spectroscopy in separate sections below. But first of all, a brief review of theoretical work on photoelectron emission is appropriate. 1 The Theory of Photoelectron Emission from Atoms and Molecules Theoretical work on gas-phase phenomena falls naturally into two categories : (i) the angular distribution of photoelectrons and (ii) the calculation of total photoionisation cross-sections. Photoelectrons show an intensity variation with angle of emission because the plane of polarisation of the exciting radiation defines an axis of quantisation. For unpolarised radiation the direction of the photon beam provides such an axis. It has been known for many years that the angular dependence for electric-dipole induced transitions obeys
D. W. Turner, A. D. Baker, C. Baker, and C. R. Brundle, Molecular Photoelectron Spectroscopy, Wiley, New York, 1970. K. Siegbahn et al., Electron Spectroscopy for Chemical Analysis, Nova Acta Regiae Societatis Scientorum, Upsaiiensis, Ser. IV, 1967, Vol. 20. K. Siegbahn, C. Nordling, G. Johansson, J. Hedman, P. F. Heden, K. Hamrin, U. Gelius, T. Bergmark, L. 0. Werme, R. Manne, and Y. Baer, ESCA Applied to Free Molecules, North Holland, Amsterdam, 1969. P i . Trans.,1970, A 268; Discussion on p.e. spectroscopy organised by W. C. Price hl and D. W. Turner. C. R.Brundle, Appl. Spectroscopy, 1971, 25, 8. Electron Spectroscopy for Chemical Analysis (or Applications).
2
the general law'
Electronic Structure and Magnetism of Inorganic Compounds
r,(@r = C[1 + pPz(C0s (1) where .Y is the axis of polarisation, 4, is the angle between the momentum vector
of the ejected electron and this axis. and [ is the asymmetry parameter which has j been defined in various ways. P2(cos4 ) is the second Legendre polynomial and is given by the expression 3 3 cos2 # - 1). Peshkin7 has shown how the above equation may be derived from quite general considerations of symmetry and has elaborated the theory to cover cross-pole and multipole ionisations. The assumptions underlying his derivation may be listed as: ( a ) the target atoms are oriented at random, ( b ) the influence of external fields is neglected, ( c ) when more than one electron is emitted, the direction of emission of the second electron is independent of that of the first. An expression for the asymmetry parameter fl was first given by Bethe for the hydrogen atom6 and generalised recently by Cooper and Zare8 and also by Berry er ctL9 to many-electron atoms, a central spherical potential field and LS coupling being assumed. Calculations using this formula have been made for the inert gases by Manson and Cooper," who show how fl varies with the energy of the exciting radiation. Buckingham er al.' have extended equation (1) to the case of diatomic molecules and have found that its form is unaltered save that the value of 1 will depend on the specific Hund coupling case involved. The equation derived by Cooper and Zare' can be seen as a special case of the more general expression given by Buckingham er al. Sichel" has extended this work to the situation where rotational fine structure can be resolved. Experimental verification of the general form of equation (1) is difficult since, in normal photoelectron work, the ionising radiation is unpolarised. The corresponding expression for unpolarised radiation is given by Peshkin' as
where d, is now the angle between the trajectory of the ejected electron and the photon beam. This formula has been shown to hold for argon by Morgenstern er c t l . , 1 3 for argon, xenon and various small molecules by Vilesov and Lopetin,14 and for zinc and cadmium atoms (in an atomic beam) by Harrison." Samson"
' H. A. Bethe, 'Handbuch der Physik,' Springer-Verlag. Berlin. ' M . Peshkin, Adr. Chem. Phys., 1970. 18, I.
1938, vol. 24.
' J . W. Cooper and

lo
l2 l3
''
l4
R . N . Zare, J. Chein. Phrs.. 1968, 48, 942; 'Lectures in theoretical physics', Gordon and Breach, New York, 1969, vol. 11. R. S. Berry, B. J. Dalton, and J. C. Tully, Phys. R e c . , 1968, 176, 95. S.T. Manson and J. W. Cooper, Phys. Rec. ( A ) , 1970, 2, 2170. A. D. Buckingham, B. J. Orr, and J. M. Sichel, Phil. Trans., 1970, A 268, 147. J. M. Sichel, Mol. Phys., 1970, 18, 95. R. Morgenstern, A. Niehaus, and M . W. Ruf, Chem. Phys. Lett., 1970,4, 635. F. I. Vilesov and S. N. Lopetin, Vesrnik Leningrad. CJnir>. (Fiz. Khim.), 1970, 64. H. Harrison, J. Chem. Phys., 1970, 52, 901. J. A. R. Samson, Phil. Trans., 1970, A 268, 141.
has discussed the form of the equation for partially polarised radiation (obtained from a grating) and has measured values of the asymmetry parameter j? for argon and molecular nitrogen. He finds that p is very near1 2 for helium, indicating that at an observation angle 4, given by cos 4 = the troublesome selfabsorption by helium in He" spectra might be eliminated.' The calculation of photoionisation cross-sections poses many problems, not least of which is the fact that the true forms of the continuum wavefunctions are not known for polyelectronic species. It is usually assumed" that continuum functions for many-electron atoms differ from those of the hydrogen atom simply by a phase factor, 6, which can be shown theoretically to relate to the quantum defect, l Y obtainable from Rydberg analysis of atomic spectra, extrapolating to positive energy. However, this information is not available for most molecules, nor indeed has the theory been shown to hold in the molecular (non-spherically symmetrical) case. Another major problem concerns the accuracy with which the ground state of the neutral atom or molecule is described. To evaluate properly the scope of the theory the best wavefunctions to hand should of course be used : but this is easier said than done, and most workers have been forced to compromise this requirement by using rather inaccurate wavefunctions. Tuckwell has, with some measure of success, calculated photoionisation cross-sections for molecular N,,' and 02,,' making use of a transformation into prolate spheroidal co-ordinates: in the case of O,, however, the quantum defect data were not available so that only relative cross-sections could be estimated. Similar calculations have been performed for atoms by Henry2' and also by M ~ G i n n , , ~ while a more empirical approach has been described by Z i l i t i ~ .Perhaps the ~~ most sophisticated many-electron treatment was reported by Brown,25who has computed a6 initio photoionisation cross-sections for the helium atom, using a correlated atomic wavefunction. The agreement with experimental data was disappointingly poor at high photon energies. A further complicating factor, in the theory of molecular photoionisation, is the variation of cross-section with energy over the vibrational structure of a photoelectron band. The calculation of the Franck-Condon factors continues to interest many workers. In particular, Tuckwell*' has shown for 0, that similar cross-sections are obtained by direct integration, without separation of the electronic and vibrational problems, and also by independent calculation of Franck-Condon factors. This provides justification for the customary use of the Franck-Condon principle in molecular photoelectron spectroscopy.' Relative cross-sections can be dealt with at a more general level. By assuming constant matrix elements between all orbital and continuum states, Cox and
&,
l9
' O
"
22
23
24
C. R. Brundle, M . B. Robin, and G . R. Jones, J . Chem. Phys., 1970, 52, 3383. M . J. Seaton, Monthly Notices Roy. Astron. Soc., 1958, 118, 504. A. Burgess and M. J. Seaton, Monthly Notices Roy. Astron. SOC., 1960, 120, 121. H. C. Tuckwell, Proc. Phys. SOC.,1 9 7 0 , 3 , 2 9 3 . H . C. Tuckwell, J . Quant. Spectroscopy Radiative Transfer, 1970, 10, 653.
25
R. J . W. Henry, Asrruphys. J . , 1970, 161, 1153. G. McGinn, J . Chem. Phys., 1970,53, 3635. V. Zilitis, Optics and Spectroscopy, 1970, 29, 617. R. L. Brown, Phys. Rev. ( A ) 1970, 1, 341.
Electronic Structure and Magnetistn of Inorganic Compounds
Orchard26 have rationalised the simple notion that the relative intensity of a photoelectron band reflects the degeneracy of the subshell ionised, and have extended the idea to the case of open-shell species. Serious deviations from simple intensity expectations may arise in the event of a transition to an autoionising state. Blake" ct al. have calculated FranckCondon factors for a model autoionising transition and have shown how very complicated band profiles may result. A more complex theory is proposed by Smith28 who invokes the Fano-Mies theory" of configuration interaction and finds an experimental example in the neon-excited photoelectron spectrum of O2 measured by Branton rt uL3' (Figure 1).
'
12
14
16
eV
Figure 1 The p.e. spectrum o f 0 , excited by the neon doublet at 736-744 A, showing the e.utensire ribrational series betu9een 13 and 16 eV whicli is not observed with He' radiation (Reproduced by permission from Phil. Trans., 1970, A 268, 77)
Relative photoionisation cross-sections may also be significantly affected by configuration interaction effects : many-electron transitions that are forbidden in the simple theory which uses the Hartree-Fock approximation become partially allowed when electron correlation is properly included. The 'mechanism' can be especially important in the case of open-shell molecules and a formally
26
'' A. J.
2a
29
30
P. A. Cox and A . F. Orchard, Chem. Phys. Letters, 1970, 7 , 2 7 3 . Blake, J . L. Bahr, J. H. Carver, and V. Kumar, Phil. Trans., 1970, A 268, 159. A. L. Smith, Phil. Trans., 1970, A 268, 169. F. H. Mies, Phys. Rer., 1968, 175, 164. G . R. Branton, D. C . Frost, T. Makita, C. A. McDowell, and I. A. Stenhouse, Phil. Trans., 1970, A 268, 7 7 .
forbidden ionisation process (producing the C211,,state of 0;) has indeed been detected by Edqvist et aL3 in the O2 He photoelectron spectrum. This followed a suggestion by Dixon and that the transition to the C2Hustate, nominally inaccessible by a simple one-electron process, could borrow sufficient intensity through configuration interaction to become observable when, correspondingly, the allowed A 2 n Uphotoelectron band should diminish in intensity from the expected value. Similar calculations have been reported for N 2 0 by Lorquet and Cadet.33 Much of the above theory can be applied directly to ESCA studies on gases but the corresponding theory for the solid state is still at an early stage of development. Siegbahn et have measured the angular distribution of electrons photoemitted from a single crystal of sodium chloride and have shown it to be a very complex function of 4, for which phenomenon the theory of Deswames and Hall36can give only a qualitative account. Angular distribution in gas-phase ESCA work has been discussed explicitly by Rao and Partha~aradhi.~ Theories relating to shake-up and shake-off processes are discussed below, but we note here that Krause3* has shown that the simple sudden perturbation approach39 is not quantitatively accurate. Various correlations with chemical shift are also discussed below but mention may be made of the calculation of the exchange splitting of the nitrogen and oxygen levels in nitric oxide.40 This fine structure arises from interaction with the unpaired electron in the highest occupied orbital (27~) which generates two states differing in energy by twice the relevant exchange integral.
~ 1 1 . ~ ~ 3 ~ ~
2 Ultraviolet Molecular Photoelectron Spectroscopy

Gas-phase u.v.-p.e. spectroscopy continues to develop at a considerable rate, both with respect to very detailed fundamental investigations of small molecules and also as regards the application of the technique to the study of larger molecules, inorganic and organic. We have already mentioned the major work of Turner et d., which contains a wealth of hitherto unpublished u.v.-p.e. spectra (though mainly of organic compounds) and extensive discussion of the problems of interpretation. There has also been a large number of review article^,^*^^^^ It appears that He p.e. spectroscopy is now over its initial teething period, the
31
32 33
34 35
36 37 38
39
40
41
42
43
0. Edqvist, E. Lindholm, L. E. Selin, and L. Asbrink, Physica Scripta, 1970, 1, 25. R. N. Dixon and S. E. Hull, Chem. Phys. Letters, 1969, 3, 367. J. C. Lorquet and C. Cadet, Chem. Phys. Letters, 1970, 6 , 198. K. Siegbahn, V. Gelius, H. Siegbahn, and E. Olsen, Phys. Letters (A), 1970, 32, 221. K. Siegbahn, V. Gelius, H. Siegbahn, and E. Olsen, Phys. Scripta, 1970, 1, 272. R . E. Deswames and W. F. Hall, Acra Cryst., 1968, A 24, 206. J. R. Rao and K. Parthasaradhi, Indian J . Phys., 1969,43, 419. M. 0. Krause, Phys. Rev., 1969, 177, 151. M. 0. Krause, T. A. Carlson, and R. D. Dismukes, Phys. Rev., 1968, 176, 37. M. G. Swartz, Theor. Chim. Acta, 1970, 19, 396. D. W. Turner, Ann. Rev. Phys. Chem., 1970,21, 107. D. W. Turner, Phil. Trans., 1970, A 268, 7. (a) A. D. Baker, Accounts Chem. Res., 1970,3, 17; (b) D. Betteridge and A. D. Baker, Analyt. Chem., 1970, 42, 43A; (c) S. D. Worley, Chem. Rev., 1971, 71, 295.
major instrumental and interpretative difficulties having been resolved. It is to be hoped, therefore, that an increasing proportion of future work will relate more to the problems of chemical, as opposed to spectroscopic or purely theoretical interest. U.v.--p.e. spectroscopy can provide a variety of information concerning molecular energy levels. For sufficiently small stable molecular species, high (or even medium) resolution measurements permit the study of vibrational motions and of vibronic and spin-orbit interactions in different states of the molecular ions: data on molecular ions are otherwise only very occasionally available from conventional U.V. emission s p e c t r o s ~ o p y . Where~ ~ ~ . ~ vibrational and other detail is not resolved, a u.v.-p.e. spectrum still yields the relative energies of certain states of the molecular ion, and in general these states are different from those sometimes observable in U.V. emission work. But the ion states studied in u.v.-p.e. spectroscopy always correspond to states that are inferable from U.V. Ryd berg absorption work. Of paramount interest to the general chemist is the approximate interpretation of u.v.-p.e. energy data using Koopmans' theorem,46 according to which the observed ionisation energies may be identified with the SCFenergies of the various occupied molecular orbitals. The theorem is not accurate, depending as it does on the cancellation of the quite distinct errors arising from the neglect of correlation effects and orbital rescaling terms."' Semi-empirical orbital energy sequences inferred from p.e. spectra are nevertheless of value to the chemist and should often prove qualitatively reliable when closely related molecules are compared. A precondition of chemical applications is, however, the unambiguous assignment of the p.e. spectra and it is with this point in mind that, in Section 2C, we choose to discuss many of the recent results in terms of various assignments criteria that are commonly invoked. The instrumental problems arising in u.v.-p.e. spectroscopy and ESCA are somewhat different in detail. However, all p.e. spectrometers possess a target area from which the electrons emitted are collected and their velocities anz!ysed. The electrons are usually examined at right angles to the direction of the exciting radiation. A. Instrumental Advances-The main advances during 1970 have been in helium radiation source technology, sample handling, and in the use of electron lenses and dou ble-focusing analysers. The general experimental arrangement necessary has been described by Turner er al. ' who actually use a 127" deflecting electrostatic analyser of 10 cm radius and a simple d.c. discharge helium lamp, the output of which is mainly the He' line at 21.22 eV. The majority of the spectra published in their monograph' were obtained with this instrument.
44
G. Herzberg, 'Spectra of Diatomic Molecules,' Van Nostrand Reinhold, Princeton,

1950. G . Herzberg, 'Electronic Spectra of Polyatomic Molecules,' Van Nostrand, Princeton 1967. T. Koopmans. Physicu, 1933, 1, 104. R . S. Mulliken. J . Chim. phis., 1949, 46,497, 675; and e . g . , W. G. Richards, internat. J . Mass Specfrometr-v Ion Phys., 1969, 2, 4 19.
J5
4b
"
The Light Source. Two methods are used to excite the radiation, the traditional method involving a d.c. discharge between aluminium electrodes' and a second method, apparently necessary when very pure helium is used, employing a microwave d i s ~ h a r g e .Careful ~ ~ ~ , ~ analyses of the lines present in a helium discharge have been given by Cairns et d 5 " and by B r ~ n d l efrom which work it ,~ appears that the most common additional lines are the Lyman a hydrogen line and the N' lines. Even very pure helium will, however, give a number of satellite lines arising from He' series, usually denoted Help, He$, etc., and lines from transitions in ionised helium, the He"a--y lines. Interestingly, it appears that the extent to which these lines occur depends upon the percentage impurity of other gases in the helium." He'P usually occurs to the extent of about 1 % in the lamp output giving a shadow spectrum about 1.88eV to higher kinetic energy.'l Lloyds2 has used this component in the radiation to help calibrate the commercial Perkin-Elmer PS 15 spectrometer, while Branton et have made use of it to measure the photoelectron spectrum of neon. The He" lines have been obtained to the extent of several percent of the He' line by several workers using low pressure and high current d e n ~ i t y . ' . ' . ~ ~ . ~ ~ He% radiation has an energy of 40.8 eV and is therefore utilised in exploring the bonding region immediately above 21.2 eV on the ionisation energy scale, the limit of He' ionisations. Massive self-ionisation of helium gas usually occurs at 24.6 eV, leading to a sharp peak in the p.e. spectrum, and at 28-30 eV the He" spectrum is swamped by the He' ionisations. Because of the very low intensity of the exciting radiation, the analyser must be adjusted to maximum transmittance with a concomitant loss in resolution. Thus, most published He" spectra have a resolution of the order of l00mV. In addition, Brundle' has pointed out that the He"P radiation may be as much as 5 % of the He% in intensity, so care should be taken to ensure that structure due to this component line is recognised. Failure to appreciate that such lines are present has led to errors in interpretation, perhaps the most serious case being that of the mercury p.e. s p e ~ t r u m , ' ~ where a strong line at 20.7 eV, originally assigned to a 5p ionisation, was queried on theoretical grounds. Re-examination of the spectrum showed that the line was in fact the result of a strongly autoionising transition induced by N' radiation. A similar case was noted in the case of benzene by Samson,54 where the band seen by a number of workers at 20.4eV can be traced to an autoionisation induced by the Lyman a hydrogen line. It has also been noted by some workers that helium lamps can exhibit slow periodic oscillations in intensity, often of several minutes total period. These
48
49
50
51 52
53
54
L. Asbrink, 0. Edqvist, E. Lindholm, and L. E. Selin, Chem. Phys. Letters, 1970, 5 , 192. G. R. Branton, D. C. Frost, T. Makita, C. A. McDowell, and I. A. Stenhouse, J . Chem. Phys., 1970, 52, 802. R. B. Cairns, H. Harrison, and R . I. Schoen, Appl. Optics, 1970,9, 605. S. Evans, A. Hamnett, and A. F. Orchard, Chem. Comm., 1970, 1282 (and refs. therein). D. R. Lloyd, J . Phys. (0, 1970,3, 629. V. Fuchs and H. Hotop, Chem. Phys., Letters, 1969,4, 71. J. A. R. Samson, Chem. Phys. LettPrs, 1969,4, 71.
fluctuations have been investigated by Asinovskii et a1. and are thought to be due to transient effects in the lamp. Surnple Handling. Methods for introducing the sample into the target chamber vary considerably. Branton et aL3 describe a slow bleed system for gases and volatile liquids whereas Weiss and Lawrences6 use a fused capillary array to give a molecular beam. Harrison uses an atomic beam generated from a furnace. Jonathan et al., in their measurements on transient species, allow the gas to pass through a silent microwave discharge before introduction into the target chamber.
Electron Analysis. The photoelectrons emitted are usually analysed by a deflecting describe a double-focusing hemispherical electrostatic analyser.s8 Branton et d3* design with two electron lenses, one at either end of the analyser, the spectrum being scanned by retardation between analyser and target chamber. Pullen et a!. describe a dou ble-focusing device, machined from aluminium, consisting of two concentric spherical sectors. Weiss and Lawrences6 use a simple deflecting analyser coupled with two lenses. Electrons are usually detected by some kind of electron multiplier, the general characteristics of which have been discussed by Archuleta and De Forest.60 The signal from the multiplier is plotted against voltage on an X-Y recorder or fed into a multi-channel analyser, thus permitting subsequent point plotting.59 A number of other types of analyser, usually of the retarding grid have been used. These frequently give highly asymmetric band profiles but continue to find favour in certain areas. 1 6 , 6 s , 6 6 , 1 4 8 Agreement between these and more reliable deflection analysers tends to be only moderately good. An einzel lens system with a very high theoretical resolution has been described by Brehm and von Puttkamer:67*68 however, the full promise of this device does not seem to be realised in practice. Some confusion apparently exists concerning the intensity pattern derived from a particular type of analyser. Basically, if the electrons are retarded after acceleration, the analyser being preset to transmit only electrons of a certain
E.
56
I . Asinovskii, V . A. Kirillin, and V . V. Markovets, Teplofiz. r j s o k . Temp. 1970,
8, 103.
5 58 59
62
bi
66
b3
M . T. Weiss and G. M . Lawrence, J . Chem. Phys., 1970, 52, 2867. N . Jonathan, D. J . Smith, and K. T. Ross, J . Chem. Phys., 1970,53, 3758. D. W . Turner, Proc. Roy. SOC.,1968, A 307, 15. B. P. Puilen, T. A. Carlson, W. E. Moddeman, G. K . Schweitzer, W. E. Bull, and F. A. Grimm, J . Chem. Phvs., 1970, 53, 768. R.J. Archuleta and S. E. D e Forest, R e r . Sci. Instr., 1971, 42, 89. M . I . Al-Joboury and D. W. Turner, J . Chem. SOC.,1963, 5141 ; 1964,4434. D. C. Frost, C. A . McDowell. and D. R.Vroom, Proc. Roy. Soc., 1967, A 296, 566. J. A . R . Samson and R. B. Cairns. Phys. Rev., 1968, 173, 80. H . J. Lempka, T . R . Passmore and W . C. Price, Prnc. Roy. Soc., 1968, A 304, 53. T. Rose, R. Frey. and B. Brehm, Chem. Comm., 1969, 1518: 1970,460. (0) . J. S. Dewar, E. Haselbach, and S. D . Worley, Proc. Roy. Soc., 1970, A 315,431 ; M ( 6 ) M . J . S. Dewar and A . J . Harget. ibid, 1970, A 315,443,457; ( c ) N . Bodor, M . J . S. Dewar and S. D. Worley, J . Amer. C h o n . Soc., 1970,92, 19; ( d ) M . J . S. Dewar, A . J . Harget, N . Trinajstic, and S. D . Worley, Tetrahedron, 1970, 26, 4505; (e) N . Bodor, M. J. S. Dewar, W. B. Jennings, and S. D. Worley, ibid., p. 4109. B. Brehm and E. von Puttkamer, 2. Natur-orsch, 1967, 22a, 8 . J . Berkowitzand W . A . Chupka. J . Chem. Phvs., 1969, 51, 2341.
134139.5cm' 134064.5crn-'
7 7
00 1 1
1 1
I 1
22
I
20
V'z
5 Ne 736A
i; p'
132222.6 c m ' from next part Ne744A
7~ of spectrum
04
03
02
0100
(b)
Figure 2(a) The p.e. spectrum of H, observed by use of a neon source (736-744 A). The rotational structure has been partly resolved. For every v' (of H,') the expected rotational lines have been indicated with the J" = 1, J' = 1 line strongest. The energy scale indicates the energy (in eV 1 o # the ejected photoelectron ( b )Detail of (a). The rotational lines have been marked J"J'. The lines that correspond to the selection rule AJ = 0, _+2have been indicated above the curve. Below the curve all lines with J" = 0 or 1 have been indicated, provided that no selection rule is valid. The intensities of the rotational lines reflect the thermal distribution of the rotational levels at room temperature with about 70% orthohydrogen (odd J) and about 30% parahydrogen (even J ) (Reproduced b y permission from Chem. Phys. Letters, 1970, 7, 549)
10
Electronic Structure and Magnetism o Inorganic Coinpounds f
energy, the spectrum obtained by scanning the potential difference between the analyser and slit is such that the intensities are not, to a first approximation, a function of the electron kinetic energy. If. on the other hand, the spectrum is obtained by scanning between the analyser plates.h8 the intensity will fall off roughly linearly with kinetic energy. Thus in this latter case intensities must be corrected for this instrumental factor. Resolution is of course a function of analyser. The best resolution obtained by typical high resolution analysers normally lies between 20 and 50 meV.* However. A ~ b r i n k ~ ~ shown that much improved resolution, of the order of has 7-12 meV. may be obtained with He radiation if extreme care is taken to eliminate stray magnetic fields, loss of equipotentials, rtc. This probably approaches the theoretical limit of resolution. which is believed to be 2- 4meV. For a given deflection analyser the resolving power E I A E is a constant ( E being the electron kinetic energy and A the resolution), so that improved resolution at low molecular ionisation energies may be realised by using lower energy radiation. Asbrink.6 for example. has used a neon source to obtain 4meV resolution on molecular hydrogen. sufficient to permit the observation of rotational fine structure (Figure 2). It is becoming increasingly recognised that the intensity pattern obtained by the use of He radiation alone may be misleading owing to the unsuspected existence of autoionising transitions. Plainly, the higher the photon energy, the less likely is the occurrence of autoionisation, but with low energy radiation from neon. or especially from argon, the effect is common and may lead to extensive vibrational progressions.3o Some discrepancies between adiabatic ionisation potentials, also obtained bj- photoionisation studies and u.v.-p.e. spectroscopy. may also be explicable on the basis of autoionisation, which is very common in threshold techniques. Ideally, a spectrum should be measured with a number of light sources of different energies in order to eliminate the possibility of anomalous intensities arising in this way. As a general note the reporters deprecate the practice of certain authors of removing noise artificially from their spectra. This is highly misleading to others and may, in extreme cases, lead to the falsification of fine structure.
B. A Compilation of U.V-P.E. References.-Listed below are those molecules for which u.v.-p.e. spectra (or ionisation energy data) have been published in 1970, together with some species of particular interest whose spectra were reported in late 1969 or early 1971. Most references concerning organic compounds are included, many of these being of sufficient spectroscopic or general chemical interest : a large number of the organic compounds referred to are also important as ligand species in metal chemistry.
0. Klemperer and M. E. Barnett, Electron Optics, C.U.P.. London. 1971. Third Edn. Chcni. P/i?..s. Letters. 1970. 7. 549. O D. W. Turner. in Physical Methods in Advanced inorganic Chemistry, ed. H. A. 0. Hill and P. Day. Interscience. London, 1968. * The resolution is usually defined experimentally as the full band width at half maximum height (fwhrn) of the A r Piline.
h80
L. Asbrink.
Rqf
Monatomic gases Inert gases Cd, Zn Diatomics
11
1, 13, 16, 49, 52, 71 15
53
H2
N2
0 2
co
1,69, 7 1 4 D2) 1, 16, 52, 72 1, 72 1, 30, 72, 73
NO
1, 74, 75
1 Br, I), 56 (C1 + DCl), 76 (F + DF)
HX
(a
NO2 H2S XeF, XCN HCN HgX2
1, 75, 77, 78 1, 79 80 81, 82 (Cl, Br, I) 1 83 (C1, Br, I)
Tetra-atomics
H,CO NH3
1 (+ HDCO, D,CO) 1, 30 ( + ND3), 84 ( f ND,) 1, 85
NF, px3 AsX, HNCO HNCS
85 86 (F, C1. Br, I), 87 (F)
86,88 86 (F, C1, Br), 89 (F), 1 1 1 (F) 86 90 90
P. Agostini, G . Barjot, G . Mainfray, and C . Manns, IEEE. J . Quantum Electronics, 1970, 6, 782. 7 1 0 AB. Cornford, D. C . Frost, C. A. McDowell, J . L. Ragle, and I. A. Stenhouse, Chem. . Phys. Letters, 1970, 5 , 486. 0. Edqvist, E. Lindholm, L. E. Selin, and L. Asbrink, Phys. Letters ( A ) , I970,31, 292. 7 3 0. Edqvist, E. Lindholm, L. E. Selin, and L. Asbrink, Physicu Scripta, 1970, 1, 25. 7 4 0. Edqvist. E. Lindholm, L. E. Selin, H . Sjogren, and L. Asbrink, Arkiu Fvsik, 1970, 40, 439. 7 5 C . R. Brundle, Chem. Phys. Letters, 1970, 5 , 410. 7 6 C. R. Brundle, Chem. Phys. Letters, 1970, 7, 317. C. R. Brundle, D. Neumann, W. E. Price, D. Evans, A. W. Potts, and D. G . Streets, J . Chem. Phys., 1970,53, 705. 7 8 0. Edqvist, E. Lindholm, L. E. Selin, and L. Asbrink, Physicu Scriptu, 1970,1, 172. 7 9 J. Delwiche and P. Natalis, Chem. Phys. Letters, 1970, 5, 564. 8 o C. R. Brundle, M. B. Robin, and G . R. Jones, J . Chem. Phys., 1970,52, 3383. R. F. Lake and H. W. Thompson, Proc. Roy. SOC.,1970, A 317, 187. E. Heilbronner, V. Hornung, and K . A . Muszkat, Helo. Chim. Arta, 1970, 52, 347. 8 3 J. H. D. Eland, Internat. J . Mass Spectrometry Ion Phys., 1970,4, 37. 8 4 M. T. Weiss and G . M. Lawrence, J . Chem. Phys., 1970, 53, 214. 8 5 G . R. Branton, D. C . Frost, C. A. McDowell, and 1. A. Stenhouse, Chem. Ph-vs. Letters, 1970, 5 , I . 8 6 A. W. Potts, H. J. Lempka, D. G. Streets, and W. C. Price, Phil. Trans., 1970, A 268, 59. 8 7 P. J. Bassett and D. R. Lloyd, Chem. Comm., 1970, 36. 8 8 P. J . Bassett and D. R. Lloyd, Chem. Phys. Letters, 1970, 6 , 166. 8 9 J. C . Green, D. 1. King, and J. H. D. Eland, Chem. Comm., 1970,1121. 9 0 J. H. D. Eland, Phil. Trans., 1970, A 268, 37.
12

Ref.
Ref
Trtrtr-ritornics i c onrtl.)
91 (F. CI. Br. 1 )
1 ( + DC-CDI
1
XCSCX XC"CX'
92 (Cl. Br, I ) 92 (Cl-Br, Cl--I, Br-I)
Prnta-atomics
HCOOH CH4 SiH,

GeH, MeX
1 1. 59. 86, 93 59 59 1 (F. CI. Br. I ) . 59 (F). 86 (F, C1, Br, I), 9 3 (F).94 (CI, Br. I CD,CI. Br).
9S(Br
GeX, SnX, TiX4 VCI, C,O, H2C=C0

CH,X,
96 (Cl, Br) 96 (Cl, Br) 96 (Cl, Br), 99 (CI)
99
1
+ various RBr)
1 1 . 86 (F, CI, Br, I), 93, 59(F)
Six4
He.xa-atomir~s
C2H4
1 (F. CI, Br, I). 86,93 (F). 96 (F. C1, Br), 97 (F).98 96 (CI. Br). 97 ( F I
ONF,
OPF,
88 151
MeCN
MeNC
H,C=CHX
I , 30.49 ( + CID,) 1.81 (+EtCN). 100 ( + CD,CN)

1
F2C=CCl CH2CICN CHC1,CN CCI,CN

MeHgX
H,C=CX2 X,C =cx HClC=CHCl F,C=CHCI F,C =CFCl
1 (F, C1, Br), 101 (F. CI) 1 (F). 101 (F. C1) 101 (F, C1) 101, 101 ( c i r and rrmiy) 101
101
HCONH, HC-C-C_CH (CHO), N2H4
101 81 81 81 83 (C1, Br, 1) 1 ( + HCONHMe. HCONMe,) 1 ( + DCFC-C=CD)
1 103 ( Me, Ph, and PhCH, derivatives)
H. J. Haink, E. Heilbronner, V. Hornung, and E. Kloster-Jensen, Hell.. Chim. A c t a , 1970,53, 1073. '* E. Heilbronner. V. Hornung, and E. Kloster-Jensen, Helr. Chim. Acta, 1970, 53, 3 3 1 . 9 3 C. R . Brundle, M. B. Robin, and H. Basch, J. Chem. Phys., 1970, 5 3 , 2196. 9 4 J . L. Ragle, I. A. Stenhouse, D. C. Frost, and C. A . McDowell, J. Chern. Phys., 1970, 53, 178. 9 5 J. A. Hashmall and E. Heilbronner. Angew. Chem. Znrernat. Edn., 1970, 9, 305. 9 6 J. C. Green, M. L. H. Green, P. J. Joachim, A. F. Orchard, and D. W. Turner, Phil. Trans., 1970, A 268, 1 1 1 . 9' W. E. Bull, B. P. Pullen, F. A. Grimm, W. E. Moddemaun, G. K. Schweitzer, a n d T . A . Carlson, Inorg. Chem., 1970, 9, 2474. " R. Manne, Chem. Phys. Letters, 1970, 5 , 125. 9 9 P. A . Cox, S. Evans, A. Hamnett, and A . F. Orchard, Chem. Phys. Letters, 1970, 7, 414. l o o D. C. Frost, F. G. Herring, C . A . McDowell, and I. A. Stenhouse, Chem. Phys. Letters, 1970, 4, 533. R . F. Lake and H. W. Thompson. Proc. Roy. Snc., 1970, A 315, 323. lo' D. A . Demeo and M. A. El Sayed, J . Chem. Phys., 1970, 52,2622. l o 3 N . Bodor, M . J. S. Dewar, W. B. Jennings, and S. D. Worley, Tetrahedron, 1970, 26,
4109.
Ref:
Hepta-atomics H2C=C=CH2
13
H2T>
B2H6
1
1
H2C Boron compounds (BHNW3 Nitrogen compounds "PF,)" N Me2C/ \ 65, 105 ( B2D,), 105,106
1, 86, 104 86 86 86 1,100

1
105 86 (F, C1, Br, I), 87 (F) PhCH2NH2 (PhCH,),NH (PhCH,),NMe 103 103 103
107
108
N
Me2C 1
;NH CH2
Transition-metal compounds 96 (CI, Br), 99 (Cl) TiX, VCl, 99 RFe(C0)3 109 (R = cis-1,3-butadiene or cyclobutadiene) Ni(CO), 89, 110 Fe(CO), 110 Ni(PF3), 89 Pt(pF,), 89, I l l v(co)6 112 Fe(hfa)3* 113, 114
104 105 106
103
Cr(hfa), Co(h fa), Al(hfa), Cr(CO),

Mo(C0)6
w(c0)6 (n-c 5 (n-c g H (n-C5 H
512
5)2
Fe Cr
5 )Z C 0
(n-C5H5)2N1
113a 113, 113a 113a 1 1 I 1 ( Mg compound), 70 1 1 1
107
108
109
110
111
112
113
114
J. Delwiche, Bull. Classe Sci., Acad. Roy. Belg., 1969, 55, 2 15. D. R. Lloyd and N. Lynaugh, Phil. Trans., 1970, A 268, 97. D. C. Frost, F. G. Herring, C. A. McDowell, and I. A. Stenhouse, Chem. Phys. Letters, 1970, 5 , 291. G . R. Branton, C. E. Brion, D. C. Frost, K. A. R. Mitchell, and N. L. Paddock, J. Chem. SOC.( A ) , 1970, 151. E. Hasselbach, E. Heilbronner, A. Mawnschreck, and W. Seitz, Angew. Chem. Internat. Edn., 1970, 9, 902. S. D. Worley, Chem. Comm., 1970, 980. D. R. Lloyd and E. W. Schlag, inorg. Chem., 1969,8,2544. I. H. Hillier, V. R. Saunders, M. J. Ware, P. J. Bassett, D. R. Lloyd, and N. Lynaugh, Chem. Comm., 1970, 1316. S. Evans, J. C. Green, A, F. Orchard, T. Saito, and D. W. Turner, Chem. P h y ~Letters, . 1969, 4, 361. ( a ) D. R. Lloyd, Chem. Comm., 1970,868; ( b ) D. R. Lloyd, Internat. J. Mass Spectrometry ion Phys., 1970, 4, 500. S. Evans, A. Hamnett, and A. F. Orchard, Chem. Comm., 1970, 1282.
=
* hfa
enolate anion of hexafluoroacetylacetone.
14
B-metal compounds
ZnMe, R,H!2
Electronic Structure and Magnetism o Inorganic Compounds f

Ref 83
X ? ( R = We. Etl
Ref
HgX, MeHgX
83 (CI, Br, I ) 83 (Cl, Br, I)
Organic compounds'
ethane and higher alkanes
Ref I
1 1
U nsat u rat ed ~ K J Yic tivri rut i t'es 1 C H C l = C H C H , C l (cis and trans) CH,=CHCHO. M e C H =C H C H O
Me Me
/
CH2=C
. Me2C=C
CHO
/
1
\
CHO CI
/
CHCI=CHCHO, MeCCI=CHCHO. C H 2 = C
1
\ CHO
MeCH=CHMe M e C H = N M e . M e N = N M e (both rrnns) Curboc!*clic~ drrirarires cyclopropane. cyclopropyl-Br. - N H 2 . -CN cyclo butane cyclo hexane
116 116, 117
1 120 124. 1 2 4 ~ 124, 124a
124, 125
124a
115
ILb
A. D. Baker, D. Betteridge, N. R. Kemp, and R. E. Kirby, Shem. Comm., 1970, 286. P. Bischof, J. A. Hashmall, E. Heilbronner, and V. Hornung, Angew. Shem. Internut.
Edn., 1969, 8, 878. E. Hasselbach and E. Heilbronner, Hell.. Chim. .3cta, 1970, 53, 684. 118 A. D. Baker and D. W . Turner, Phil. Trans., 1970, .4 268, 131. 1I9 R. Gleiter, E. Heilbronner, and V. Hornung, Angen. Chem. Infernat. Edn., 1970, 9, 901. 120 P. Bischof, E. Hasselbach, and E. Heilbronner, Angew. Chetri Internat. Edn., 1970, 9, 953. I21 J . A . R. Samson, Chem. Phys. Letters, 1969, 4, 251. 122 L. Asbrink, 0. Edqvist, E. Lindholm, and L. E. Seiin, Chem. Phys. Lt,rrers, 1970, 5 . 192. 609. 123 E . Heilbronner. V. Hornung. H. Bock. and H. Alt. Angew. Shem. Internut. Edn., 1968. 8, 524. 121 P. Bischof, J . A . Hashmall, E. Heilbronner, and V. Hornung, Helr. Chim. Acta, 1969, 52, 1745. 1 2 4 a D . A . Demeo and A . J. Yencha, J . Chem. Phys., 1970, 53,4536.
11'
124a norbornane and related species 124, 128, 124a 125 adamantane and related species bullvalene and related species bicyclo[2,2,2]octane and related compounds cyclic olefins 129 130 126, 128 131
15
Benzene and its dericatiivs ben Zen e toluene Turner et al.' have also published a very large number of benzene derivatives, too many to list individually here. They include halogenobenzenes up to perfluorobenzene; halogenotoluenes; PhCF, and simple derivatives ; PhNO,, PhNO, and halogeno derivatives; PhCN and PhCHO; PhNH, and various N - and ring-substituted anilines ; PhOH and various ethers, PhOR ; naphthalene Heterocyclics
1 , 119,121, 122
1
115
1,115, 118
1.118
c 1
C N H 1
pyridine Cl 1 (+ Me subst. derivatives), 118, 119 1 ( + 3- and 4chloropy ridines)
lZ5
P. Bischof, J. A. Hashmall, E. Heilbronner, and V. Hornung, Tetrahedron Letters,

1970, 1033.
126
P. Bischof, J . A. Hashmall, E. Heilbronner, and V. Hornung, Tetrahedron Letters,

1969,4025.
'*' E. Heilbronner and K. A. Muszkat, J. Amer. Chem. Soc., 1970, 92, 3818.
lZ9
130
131
P.Bischof, R. Gleiter, and E. Heilbronner, Helo. Chim. Acta, 1970, 53, 1425. N. Bodor, M . J. S. Dewar, and S. D. Worley, J. Amer. Chem. SOC.,1970,92, 19.
P. Bischof, R. Gleiter, E. Heilbronner, V. Hornung, and G . Schroder, Helv. Chim. Acta, 1970, 53, 1645. P. Bischof and E. Heilbronner, Helo. Chim. Actu, 1970, 53, 1677.
16

Ref:
1
1, 118, 119
126
127
C. Assignment Criteria.-Culculntions. The information available from u.v.-p.e. spectroscopy has renewed the interest of chemists in molecular orbital calculations of both the ab initio and semi-empirical types. These are discussed in detail elsewhere in this report, but some general comments seem appropriate in the present context. The most rigorous approach, within the Hartree-Fock approximation, is the so-called direct method, which requires separate calculations on the ground state of the neutral molecule and also on each accessible state of the molecular ion. The differences between the calculated ground state and ion state energies will not correspond exactly to the measured ionisation energies since correlation effects have not been taken into account.* An instructive but daunting example is that of molecular nitrogen, where an extensive ub initio LCAO-MO SCF of N z and N, failed to predict correctly the ground state of the molecular ion, presumably because of the neglect of correlation terms. However, more serious errors are often occasioned by failure, in the individual calculations, to realise the Hartree-Fock limit. Very few ab initio calculations of the direct type have in fact been reported during 1970, the sole example in connection with u.v.-p.e. spectroscopy being an investigation of NO, by Brundle et al. Calculations on the neutral molecule alone have been much more common. Koopmans theorem4 then permits the prediction of ionisation energies as the theoretical SCF one-electron eigenvalues for the appropriate molecular orbitals. However, Koopmans theorem involves certain well-known approximation^^^ (the neglect of orbital rescaling effects as well as the correlation terms) which invalidate this approach for ion states close in energy, even when the HartreeFock calculations for the neutral molecule ground state is exact. In practice, the use of Koopmans theorem in connection with accurate SCF theory leads to estimates of ionisation energies that are usually 2-1070 too large. The main
13*
P. E. Cade, K . S. Sales, and A . C. Wahl, J . Chem. Phys., 1966,44, 1973.
* However, tolerance limits can usually be placed o n this error.
17
contribution of this approach to the assignment problem is to provide a rough ordering of ion state energies rather than to make detailed quantitative predictions of p.e. spectroscopic data. The ub initio theoretical interpretation of molecular ionisation energies is, of course, correspondingly less reliable when rather limited A 0 basis sets are used and the SCF calculation is remote from the Hartree-Fock limit. Bearing in mind problematical cases such as those of N,I3' and C0,,133 it does not seem constructive to apply a scaling factor to theoretical energies as an attempt to improve numerical agreement with experiment. * 0*93 Ab initio calculations using Koopmans' theorem have been performed by Brundle et ~ 2 1 to ~assist assignment of their p.e. spectra of the fluoromethanes . ~ and of XeF," [Figure (311. Published SCF results have been invoked for this
'
Figure 3 The p.e. spectrum of XeF, in the range 11-21 eV. The upper curve was obtained using the He" line (40.82 eV) whereas the lower full curve was obtained using the He' line (21.2 eV). The intensity-corrected He' spectrum is shown as the dashed curve. Features marked Xe are due to ionisation of xenon atoms (Reproduced b y permission from J. Chem. Phys., 1970,52, 3383)
'33
S. D. Peyerimoff, R. J. Buenker, and J. L. Whitten, J. Chem. Phys., 1967, 46, 1707; A. D. McLean and M. Yoshimine, I.B.M. J. Res. Devel. supplement, 1967; J . A. Horsley and W. H. Fink,Proc. Phys. SOC. 1969,2, 1261. (B),
18
purpose in other u.v.-p.e. investigations, by Lloyd and Bassett for NF3,88by ' Lloyd and Lynaugh for diborane'" and borazine, by Bull et ~ 1 . ~ for CF,, and also by Branton er aL3'." in the case of ethylene. An interesting case is the u.v.-p.e. spectrum of benzene, where by comparison with the spectra of a number of isoelectronic heterocyclic molecules. the first two bands were both assigned to ionisations from 7c levels.' Calculations, however, indicated that at least one D level should lie between the two 71 levels.134Two additional bands were reported by M ~ m i g n y but ~ ' ~ these were later shown by Samson' to arise from impurity lines in the source. Thus it seemed that Koopmans' theorem was seriously breaking down here, but careful analysis of a very high resolution benzene u.v.-p.e. spectrum by Asbrink er (11.~'~ (Figure 4) has shown that the second band arises from a 0 level and the third from the second n level, in accord with the most accurate calculations.
9.6
P.
9.5
9.4
9.3
9.2
eV
m Lo
I - L - _ _ L - u ~
11 9
11 8
11 7
11 6
115
eV
Figure 4 The ribrational detuil in the first (upper) and second (lower) He' p . e . bands of benzene ( The numbers <girenon the ypectra are in meV) (Reproduced by permission from Chrm. Plixs. Letters, 1970.5, 609)
Accurate calculations for larger molecules are impracticable given the present state of compu ter technology, and various types of semi-empirical approach have been tried, usually invoking Koopmans' theorem4' to help form some idea of the energy sequence of ion states. It is exceedingly difficult to evaluate this kind
13J
135
M . D. Newton, F. P. Boer, and W . N. Lipscomb, J . Amer. Chem. SOC., 1966,88, 2367. J . Momigny and J. C. Lorquet, Chem. Phys. Letters, 1968, 1, 505.
19
of work. Certainly, any assignment of a complex p.e. spectrum which depends solely on an approximate MO calculation must be viewed with particular suspicion. Semi-empirical calculations have been used extensively in the field of organic u.v.-p.e. spectroscopy. The subject has been recently reviewed by W ~ r l e yand ~ '~ and of Heilbronner attention is drawn especially to the work of Dewar et et u1.46,82,9 1 , 9 2 , 1 2 3 - 1 2 8 , 1 3 0 . 1 3 1 who use ZDO or extended Huckel theories to predict ionisation energies of outer orbitals. Frost et ~ 1 . ' ' ~employed CNDO calculations to order the levels in acetonitrile and methylacetylene, but made use of the INDO method for borazine,106 whilst Lloyd and Lynauch'" have investigated syn-B-trifluoroborazine using a CNDO calculation. Such calculations are of course rarely conclusive and usually further evidence is adduced in support of the provisional assignment : this additional evidence is often at variance with the predictions of the approximate MO treatment.
Fine Structure. Ionisation from a non-degenerate orbital in a closed-shell molecule may only excite single quanta of a totally symmetric vibrational mode. Non-totally symmetric modes are excited in double quanta. 1 3 7 This means, especially in smaller molecules, that vibrational assignments may often be made with some degree of certainty and the resultant frequencies compared with those in the neutral molecule. It is usually argued7' that increase in vibrational frequency of a given mode in a particular ion state as compared with that in the neutral molecule will indicate ionisation of an anti-bonding electron, and conversely a decrease in frequency will indicate ionisation of a bonding electron. Furthermore, if a molecule possesses a number of totally symmetric vibrational modes, the probability of exciting a particular vibration can be related to the type of molecular orbital from which ionisation occurs. For example, ionisation from an orbital concentrated in the B-H bond regions of diborane is likely to excite the symmetric B-H stretch etc., and Lloyd and Lynaughlo5 have used such arguments to support their assignment of the diborane u.v.-p.e. spectrum. The first p.e. band of NH,s4 shows strong excitation of the a, inversion mode ( v 2 ) ,which leaves little doubt that it is the a, lone-pair orbital that is ionised, in since the 2A1 ion state (2Al;. D3h)produced is expected to have a planar equilibrium geometry. Other examples are given by Turner et al.' In the hydrogen-containing molecules, the study of the deuteriated analogues frequently proves helpful. Thus, if a stretching frequency is little altered on deuteriation, the normal mode excited must be one not involving the stretching or deformation of bonds to hydrogen and this may be of assistance in identifying the mode concerned. Branton et have discussed the u.v.-p.e. spectra of ethylene and [2H4]ethylene while these authors and Weiss and Lawrence84 have both measured NH, and ND, . Turner et al.' give a number of additional examples, including H,O and D20, formaldehyde and [2H,]formaldehyde, and
"' S. D. Worley,
13'
Chew. Rev., 1961, 71, 295. See ref. 45; * G. Herzberg, 'Infrared and Raman Spectra of Polyatomic Molecules', Van Nostrand, Princeton, 1945.
20
acetylene and ['HJacetylene, to illustrate the utility of the technique. The parallel investigation of the deuterio-species is also of value by virtue of the Teller-Redlich theorem' 3 7 which may give information about the geometry of the ion. The theorem has been used by Weiss and Lawrences4 to show that the ' A , state of NH,' is planar. Cornford et ul.' l a have performed a thorough vibrational analysis under much improved resolution of the hydrogen and deuterium u.v.-p.e. spectra and the derived spectroscopic constants are compared with various calculations for H 2 + and D 2 + . h b r i n k et al.69,'2--74*7g have also reported high resolution spectra with complete vibrational analyses for a number of small molecules and in this way have shown" for 0, that a hitherto undetected A2n,state can be seen at 17.045 eV (Figure 5).
13 0
12 5
12 0
Figure 5 (Upper) The He"p.e. spectrum ofO,,frorn 16 to 28 eV. Theprogression 12-13 eV has been omitted. (Lorver) The He' p . e . spectrum of 0 ,.from 12 to 13 eV at very high resolution showing spin-orbit splitting (Reproduced by permission from Phj-sica Scripta, 1970, 1, 2 5 )
The occurrence of distorted bund shapes in photoelectron spectra is of very considerable interest. These may arise in four possible ways :
(i) Autoionisation. Autoionisation in He' p.e. spectroscopy involves excitation of the molecule to a state lying about 21 eV above the ground state of the neutral molecule. If this state is sufficiently long-lived to execute vibrational motion before decay, the derived vibrational profile will be radically different from that which would be seen from the direct ionisation. The neon-excited molecular
Photoelectron Spectroscop-v
21
oxygen p.e. spectrum is reproduced in Figure 1 3 0 and three distinct vibrational band maxima may be discerned in the ionisation to the 21'lg state. This may be compared to the rather different He' spectrum reproduced by Turner et al.' Another case reported is that of carbon tetrafluoride where the He" p.e. spectrum is better resolved to the base-line than the He' spectrum, strongly suggesting an autoionising transition in the latter case.93
(ii) Predissociation. The p.e. spectrum of hydrogen cyanide' is reproduced in Figure 6. It can be seen that the band of adiabatic ionisation energy at 19.0 eV shows a distinct vibrational progression which decays to an indistinct mound at
600
t 21
0
I
20
19
18
17
eV
16
1 5
14
Figure 6 The He' p.e. spectrum o HCN showing decay of vibrationalfine structure caused f
by pr edisso cia t ion
(Reproduced by permission from 'Molecular Photoelectron Spectroscopy,' Wiley,

New York, 1970)
about 20.4eV. This decay is attributed to rapid dissociation of the molecule above this energy, which correlates with the appearance potential of CN' in photoionisation studies. A similar effect may be observed in the spectrum of sulphur hexafluoride.1 , 8 6 * 1O 4 Photoionisation and electron impact data concerning appearance potentials have frequently been used to explain loss of vibrational structure, and good examples are found in the u.v.-p.e. spectra of the hydrogen halides given by Turner et al. The second band in each of these spectra corresponds to ionisation to a 'C+ state. That of HCl shows pronounced wellresolved fine structure, that of HBr a typical predissociation profile with only four well-resolved elements, while in HI the band is very indistinct, suggesting
22
that in this case the state is crossed by a repulsive state at or below the r = 0 level. A clear correlation with the appearance potential of X + can be given. Another example of some interest is methane, whose spectrum38 is reproduced in Figure 7 ; the decay of fine structure similarly coincides with the appearance of
8300 ~
CHL
6 000
-
,/
p
c
6000-
eV
1600
15 CIC
SINDING
l i 00 ENERGY
3 00
Figure 7 The He p . e . spectrum of methurie under high resolution (Reproduced by permission from Phj*sicu Scripin. 197 1. 3. 13)
CH, in photoionisation experiments. Further illustrations may be found in the in U.V.p.e. spectrum of hydrogen sulphide measured by Turner et d., that of diborane reported by Rose et a1..6 and also in the spectra of methyl bromide obtained by Potts et and by other research groups.
(iii) Kbronic Eflects. Ionisation from a degenerate subshell of a closed-shell system leads to an ion state possessing orbital degeneracy, which in the case of non-linear molecules will be subject to Jahn--Teller distortions. The Jahn--Teller (or vibronic) forces in the molecular ion may manifest themselves in essentially two ways in u.v.--p.e. spectra. If the vibronic interactions are strong, the vibrational envelope of the p.e. band may be highly irregular, and in extreme circumstances may display a double (or even triple) maximum. Where these interactions are relatively weak all that may be observed is vibrational fine structure corresponding to excitation in single quanta of a non-totally symmetric (degenerate) vibrational mode.* The first unequivocal example of an actual Jahn--Teller splitting in a p.e. band was that r e p ~ r t e d ~ the t , ionisations of methane in the 13--16.5eV region for (Figure 7). The theory of vibronic interactions in the first 2T2state of CH, has subsequently been extensively investigated. 1 4 3 In general, the theory for
J . W. Rabalais. T. Bergmark. L . 0. Werme. L. Karlsson. and K . Siegbahn, Physica Scriptu, 1971, 3 , 13. 13 A. D. Baker, C . Baker, C. R. Brundle. a n d D. W. Turner, Internat. J . Mass. Spertromerry Ion Phys., 1968, 1, 285. G . S. Handler and H. W. Joy, Internat. J . Quantuin C h e m . , 1969, 529. J. Arents and L. C. Allen, J . Cherti. P h j s . , 1970, 53, 73. Id F. A. Grimrn and J . Godoy, Chem. Phys. L e t t . . 1970, 6, 3 3 6 . R. N. Dixon, Mof. Phvs., 1971. 20, 81. Non-degenerate modes, other than the totally symmetric one, may also in principle be excited in the ionisation of singly degenerate orbitals if !he vibronic coupling is strong enough.
Photoelectron Spectroscop-y
23
tetrahedral molecules is much complicated by the fact that more than one normal mode can be vibronically active (both e and t , for T states). On the other hand, simple tetrahedral molecules, MX, , possess only one totally symmetric normal vibration so that the vibronically induced excitation of degenerate modes should be easier to detect.'44 Indeed, Bull et al. have observed vibronic fine structure (associated with thee normal mode) in the third p.e. band of CF,, which permitted an unambiguous assignment to the 2 E ion state." Many small cyclic organic molecules appear to show pronounced Jahn-Teller structure in their u.v.-p.e. spectra. Particularly good examples are provided by c y ~ l o p r o p a n eand cyclobutane,' 2o the first p.e. bands of which are very '~~ substantially split, probably as a result of vibronic distortions of the ' E ion ground states. Extremely careful vibrational analyses of the BF, u.v.--p.e.spectrum, by Lloyd and Ba~sett,~' of the benzene spectrum by Asbrink et al. ' 2 2 (Figure 4) and have clearly demonstrated the excitation of doubly degenerate vibrations and emphasised the significance of such fine structure in connection with the assignment problem. In particular, Asbrink et ul. were able to establish with little doubt that the energy ordering of the lowest states of C6H6+is 2El,(n)> 'E,,(o) > ,A,,(n) [in agreement with theoretical sequence of orbital energies, le,,(n) > 3e2,(a)> l ~ ~ ~ ( The]u.v.--p.e. spectrum of NH384 n) . shows a distinct plateau in the band arising from ionisation of the e molecular subshell (but there is no definite splitting of this band). The more regular profile of the corresponding band in the ND,84 spectrum may reflect the decreased frequency of the e normal vibration in this molecule. But a more convincing example of such an effect is provided by a comparison of the u.v.-p.e. spectra of CH, and SiH,,59 the t , band of the latter being much less irregular.
(iv) Multiplet and Spin-vibronic Structure. The u.v.-p.e. spectra of molecules containing heavy atoms may exhibit multiplet fine structure arising from spinorbit interactions in orbitally degenerate states of the molecular ions. This spectroscopic detail can often substantially facilitate the interpretation of complex spectra by indicating both the localisation characteristics of the subshells ionised and also the orbital degeneracies. The low energy structure in the CCl, and CBr, spectra (Figure S)96 are instructive in this connection. The expected ionisations from essentially halogen t , , t,, and e orbitals are difficult to identify in the CCl, spectrum, but a comparison with the spectrum of CBr, is immediately informative. The assumption that the p.e. bands are due to ionisation of predominently halogen orbitals is confirmed, and a theoretical analysis of spinorbit interactions in the ,T2 and ,Ti ion states permits assignment of both spectra.96 A particularly powerful example of this kind is provided by the u.v.-p.e. spectra of the mercury dihalides, HgX,, reported by Eland83 (Figure 9). Molecular ion states subject to multiplet splitting are at the same time susceptible to Jahn--Teller effects. In small molecules, where vibrational fine
44
'45
K . Nakamoto, 'Infrared Spectra of Inorganic and Coordination Compounds,' 2nd edition, Wiley, New York, 1970. H. Basch, M. B. Robin, N. A. Kuebler, C. Baker, and D. W. Turner, J . Chem. Phys., 1969, 51, 52.
24
14
13
(0)
12
11
14
13
12
11
10
(b)
Figure 8 The low ionisation bands in the He' p.e. spectra of ( a )CCI, and ( b )CBr, . Multiplet structure is clearly erident in ( b ) [Reproduced by permission from 'Molecular Photoelectron Spectroscopy,' Wiley, New York. 1970: Phil. Trans. 1970. A 268. 1 I I]
structure is inherently resolvable, the multiplet structure may be much complicated by concomitant vibronic detail: the form of the fine structure actually observed will depend on the relative magnitudes of spin-orbit coupling and vibronic coupling. Varying degrees of this spin-cihronic structure are observed in the band systems of the u.v.--p.e. spectra of the methyl halide^',^',^^,'^ 9 5 (Figure 10) that arise from ionisation of the halogen p n lone-pair electrons (of e symmetry). The details have been discussed by Ragle et dy4 the light of the in spin-vibronic coupling theory of Longuet-Higgins ct The Me1 and MeBr spectra resemble each other in showing two strong bands with the separations expected for the ' E , and 2 E , multiplet states of the ions, but there are significant differences in the relative intensities and the vibrational fine structure accompanying these bands. The MeBr vibrational structure is attributed by to the excitation of e normal modes through relatively weak JahnRagle et Teller interactions. These degenerate vibrations are apparently not excited in the Me1 case, where the much attenuated fine structure is assigned* to a, normal modes, essentially because spin-orbit interactions are here sufficiently large to quench vitvonic coupling. The highly complex band profile observed for the corresponding ionisation of MeCl is the result of serious competition between spin-orbit and Jahn-Teller forces of similar magnitude. Complicated band
H . C. Longuet-Higgins, U . Opik, M . L. H. Price, and R . A. Sack, Proc. Roy. Soc., 1958, A 244, 1 . * However, the vibrational assignments given by these authors are at variance with those advanced by Potts er a1.a6and by Turner et al.' It should also be pointed out that Ragle et a/.94 fail to detect some important fine structure in the MeCl spectrum (cJ Figure 1 1 ) .
'"
25
!6
14
12
10
Figure 9 The He' p.e. spectra ofthe rnercury(I1) halides (Reproduced by permission from Internat. J . Mass. Spectrometry Zon Phys., 1970,437)
c
I
I
1 1 1 1
'
I cm'l 1 0
'
2000
4000
(c)
cm-l
2000
4000
1 ' 1 ' 1 6000 8000 10000
(a)
Figure 10 Detail of thejrst band in the He' p.e. spectra of (a) MeCl (b) MeBr (c) MeI, showing the alteration of$ne structure as the ratio between spin-orbit splitting and vibrational spacing increases (Reproduced by permission from J . Chem. Phys., 1970,53, 178)
27
1. 18
11.7
11.6
11.5 eV
11.4
11.3
11.2
Figure 11 The first band in the He' p.e. spectrum of MeCl
(Reproduced by permission from 'Molecular Photoelectron Spectroscopy,' Wiley, New York, 1970)
structures for halogen lone-pair ionisations are also encountered in molecules of low symmetry where the p x and p y halogen pn orbitals are no longer degenerate. Linear molecules may exhibit particularly simple multiplet fine structure, since first-order Jahn-Teller terms vanish. Thus, the ionisation of the mainly chlorine ng subshell in HgC1283 gives a p.e. band with a clearly discernible spinorbit splitting (Figure 9). Also of importance in this connection are the u.v.-p.e. spectra of the mono- and di-halogenoacetylenes reported by Heilbronner et and the spectra of the cyanohalides described by both Lake and Thompson8' and also by Heilbronner et aLS2 A particularly interesting case is the u.v.-p.e. spectrum of XeF, (Figure 3),*' measured by Brundle et al., where the effects of spin-orbit coupling at the xenon site are clearly evident.
~ 1 . ~ ~ 9 ~ ~
Empirical Approaches. It is often supposed that the relative integrated intensities of bands in the p.e. spectrum of a closed-shell molecule approximately reflect the degeneracies of the subshells that are ionised :I this has been discussed recently by Cox and Orchard,26 who consider also the case of open-shell molecules. The assumption of a simple relationship between orbital degeneracy and ionisation cross-section was used extensively in the original assignments of many u.v.-p.e. ~pectra,~' it has become increasingly apparent that this approach is frebut quently invalid. The intensity criterion may often prove reliable for ionisations
28
16
18
20
IONIZATION P O T E N T I A L
eV
Figure 12 The He' p.e. specrrum qf BF, (Reproduced by permission from Cliem. Comm., 1970. 36)
of molecular orbitals of similar energies and localisation properties,* but in general should not be invoked as a basis for assignment in the absence of supporting evidence. The u.v.-p.e. spectrum of BF, (Figure 12) provides a cautionary example. The first p.e. band is substantially more intense than the second, which and also Lloyd and Ba~sett,~' assign these bands to 2 E to lead Potts et and ' A ion states, respectively: however, it seems more likely on theoretical grounds, and by analogy with isoelectronic species such as N0,45,147+ and C 0 3 - , 1 4 8that the ground state of BF,' is 2A2'. The relative probability of realising either of the low-lying ' E ' and 2E" states may be much influenced by vibronic interactions in the ion and by configuration interaction (in C,") between these two states.
R. Lefebvre and E. Ressayre, Theor. Chim. Acra, 1970, 18, 391. J . F. Olson and L. Burnelle, J . Amer. Chem. Soc., 1970,92, 3659 and refs. therein * However, even in these circumstances, the occurrence of autoionisation may lead to quite misleading band intensities. i The theoretical ground state of N O , is found to be 2 A 2 ' with 'E" only very slightly higher in energy.'47
14'
1' 4
29
A number of workers have adopted a more chemicalapproach to the assignment problem by careful comparison of a series of closely-related (e.g. isoelectronic) molecules in order to identify reasonable patterns of changing orbital . energy. Thus, Potts et ~ 1 assign~the ~u.v.-p.e. spectra of the series NX,, PX,, and AsX, (X = F or Cl), partly by internal comparisons but partly by comparison with the analogous trihalogenomethanes, CHX, . The interpretation of the spectra of the halogenomethanes themselves, CH,X,-, (where X = F, C1, or Br), was also much facilitated by a careful analysis of trends in orbital ionisation . ~ ~ energies. Green et ~ 1 have employed a similar empirical approach to a series of MX, species, where X = C or Br and M = C, Si, Ge, Sn, or Ti, and show how 1 simple overlap considerations and careful treatment of multiplet fine structure can assist the assignment of the u.v.-p.e. spectra of simple halide species. The interpretation advanced by Cox et ~ 1for. the spectrum of VCI, depended ~ ~ Turner upon the assignment of the TiCI, spectrum given by Green et et a/. were able satisfactorily to explain the u.v.-p.e. spectrum of HCN only after an examination of acetonitrile: the CN n level and the highest 0 level, apparently of almost identical energies in HCN, were clearly distinguished in the MeCN spectrum. The relative ordering of the lone-pair and highest n energy levels of pyridine l 8 was similarly not clear until the u.v.-p.e. spectrum of 2-trimethyl~ilylpyridine~~ also been examined. The assignment of the u.v.-p.e. had spectra of Ni(PF,), and Pt(PF,), was based in part on a close comparison with p.e. data for Ni(CO), and the free ligand PF,: however, the veracity of the Pt(PF3), spectrum has been questioned, and the assignments disputed. Heilbronner et al. have investigated non-bonding and lone-pair interactions in a wide series of related organic molecules, using very simple overlap arguments to assign the observed p.e. bands :O 8 > l 1 6 v 1 24- 2 8 * 1 3 1 these interactions appear to be quite considerable.
791
D. Complementary Techniques.4ther methods of measuring ionisation energies are well established and a comparison between p.e. spectroscopic data and the information derived from these complementary techniques is clearly desirable. The most important methods are, without doubt, photoionisation, electron impact, and mass spectroscopy : these yield appearance potentials for molecular ions and fragments and may, by measurement of ionisation efficiency, provide information about higher energy ionisation processes. Such experiments lead to estimates of ionisation energies that are usually intermediate between the adiabatic and oertical ionisation energies determined by u.v.-p.e. spectroscopy. However, in certain circumstances, where very large changes in molecular geometry take place on ionisation, the Franck--Condon factors for production of the lowest vibrational states of the molecular ion may become extremely small : the measurement of photoionisation with accompanying autoionisation, will then yieId more reliable estimates of adiabatic* ionisation energies.
* The adiabatic ionisation energy corresponds to the 0 4 vibrational component of the photoelectron band. Where this feature is not clearly discernible it is better to define the threshold energy for an ionisation process.
30
Another method of particular importance for rather small molecules is the investigation of far-u.v. Rydberg series. Special mention should be made of the extensive studies by Lindholm of the relationship between Rydberg spectroscopy and u.v.-p.e. spectroscopy. Unambiguous assignments of Rydberg progressions are often not possible, but ionisation energies can of course be measured with great accuracy from series limits. Where the assignments are not in doubt (as in the N, and Me1 Rydberg spectra, for example), the gases can be very useful for calibration purpose^.^'
E. Discussion of some Selected Results-Compounds qf the Main-group Elemuits. A wide range of simple non-metal halides have been investigated. Of obvious general interest are the trends in molecular orbital energies (as deduced using Koopmans' approximation") with change of halogen atom (X) in series of compounds such as BX,(X = F, C1, Br, I), CX,(F, C1, Br), and PX,(F, CI, Br),* and also with variation of central atom in the following series :
NH, PH3 ASH, NX,
PX 3
AsX, [X = F. Ci]
CH4 SiH, GeH,
cx4
Six,
GeX,
SnX,
[X = Cl,Br] The trends in orbital energies in Group V, in particular. show some intriguing irregularities. Many of these Group V molecules are important ligand species (Lewis bases) in transition-metal chemistry and u.v.-p.e. spectroscopy can provide useful information concerning this function. A comparison of the spectra of NH,, NF,. PH,. and PF,, for example, is particularly instructive in this connection. Whilst the ionisation potentials of such molecules. which relate to the N , ((T 'lone-pair') orbitals. can be measured by other techniques, u.v.-p.e. spectroscopy enables us also to investigate possibly important, lower-lying donor levels. The boron trihalides. and also certain of the Group I V species above, are of interest as Lewis acids, and the thorough examination of such molecules, coupled with parallel studies of Lewis base species, is a necessary prerequisite for the investigation by u.v.-p.e. spectroscopy of the bonding in donor-acceptor complexes. Many such complexes should prove amenable to the u.v.-p.e. technique : indeed. Lloyd and co-workers have already made progress in this direction by studying the compound PF,BH,.'" A rather special instance of this type of investigation is that of Bassett and Lloyd, who have reported the u.v.-p.e. spectra of ONFJ8' (Figure 13) and OPF,'" (a free oxygen atom falling within the general definition of a Lewis acid). The complete correlation that becomes possible between the occupied orbitals of the donor and acceptor species and those of the complex is both elegant and novel.
lJ9
SF, SeF, TeF, UF,
I5O
"'
E. Lindholm, .4rkiu Fysik, 1969, 40,97ff. I. H. Hillier, J . C. Marriott, V . R. Saunders, M. J . Ware, D. R . Lloyd, a n d N . Lynaugh, Ckem. Comm., 1970, 1586. P. J . Bassett, D. R . Lloyd, I . H . Hillier. and V . R. Saunders, Chern. Phys. Lerrers, 1970, 6, 253.
* However. the detailed assignments of the u.v.-p.e. spectra of the B X , and P X , species are not yet firmly established.
31
15 20 IONIZATION POTENTIAL, eV
Figure 13 The He' p.e. spectra of NF, and ONF, (Reproduced by permission from Chern. Phys. Letters, 1970, 6 , 166)
The work of Potts et aLS6on the Group VI hexafluorides and of Green et ~ 1 on the Group IV tetrahalides also has significance elsewhere. The high (cubic) symmetry of these halides permits a detailed analysis of halogen-halogen interactions, the results of which have a clear relevance to problems concerning the electronic structures of simple octahedral and tetrahedral transition-metal complexes. Compounds of the metallic main-group elements have been little investigated by u.v.-p.e. spectroscopy, presumably because of the involatility of the majority of such materials. However, Elands3 has obtained the He' spectra of the dihalides of mercury (Figure 9) together with those of the methyl mercury halides, MeHgX, and the Group IIB alkyls HgMe,, HgEt,, and ZnMe,. The spectra are fascinating in a number of respects, but most of all, from the inorganic viewpoint, because the ionisations of the mercury 5d electrons (and the zinc 3d electrons) are clearly identifiable. The 5d'O shell of the mercury atom is apparently strongly perturbed by >pin orbit coupling and probably also by covalent effects. On the orbital energy scale, these perturbed 5d orbitals lie between the 'outer'
32
valence MOs, compounded mainly of mercury 6s, 6 p AOs and halogen n p AOs, and the inner valence MOs of predominantly halogen ns character. Thus. on purely energetic grounds alone. it seems likely that the 5d shell of mercury is significantly involved in the bonding in these species.
Transition-metal Compounds. The relative involatility of most compounds of the transition elements imposes extreme limitations on the investigation of their electronic structures by vapour phase u.v.-p.e. spectroscopy. The available data relate to rather volatile materials, especially organometallic compounds. The u.v.-p.e. spectra of all the common binary monomeric carbonyls have by now been reported, and exhibit many interesting features. The hexacarbonyls of Cr. Mo. and W have very similar spectra (o.R. Figure 14), each displaying a
L A
f 600
>
21
20
19
18
17
16
15
cv
14
13
12
11
1 0
Figure 14 The He p.e. spectrum of Mo(CO), shoning the separation of predominandv metal d-ionisation at 8.5 eV from essentially carbonyl structure abozv 13 eV (Reproduced by permission from Molecular Photoelectron Spectroscopy, Wiley, New York, 1970)
single, relatively smooth p.e. band corresponding to ionisation of the essentially metal d ( t 2 J electrons, which is well separated from the structure due to ionisation of non-bonding and bonding MOs mainly localised o n the CO ligands. The t2p ionisation energies are almost identical (each ca. 8.4 eV), within experimental error, in the three molecules. This is quite remarkable at first sight, but is intelligible in view of the closely similar d ionisation energies of the free metal atoms. 5 2 The u.v.-p.e. spectrum (Figure 15) of the open-shell species, V(CO),, l 2 shows some structure in the corresponding d p.e. band, which may be understood in terms of the separate production of the different states arising from the (t,.J4 configuration of the molecular ion. The first bands in the spectra of Ni(CO), and Fe(CO)5 (Figure 15) merit special comment in connection with ligand field theory. The relative intensities of these d bands confirm, in a rather elegant and (e)4(e)4. manner, the expected outer electron configurations. (e)4(t2)6 respectively. The inferred relative energies, t , > e, for the Ni(CO), d-orbitals are
15
C. E. Moore, Atomic Energy Levels, Circular no. 467, Nat. Bur. Stand., Washington D.C., vols. 1-111, 1949, 1952, and 1958.
33
C r (CO),
Fe
L
8
I I 1
10
9 8 IONIZATION POTENTIAL, cV
11
10 IONIZATION
9
POTENTIAL, eV
Figure 15 Details of the He p.e. spectra of ( a ) Cr(C0)6 ( b ) Fe(CO), ( c ) V(CO), (d) Ni(C0)4 showing in each the region of predominantly d-ionisation [Reproduced by permission from (a) Molecular Photoelectron Spectroscopy, Wiley, New York, 1970; (b) and (d) Znorg. Chem., 1969,8,2544; (c) Chem. Ph,vs. Letters, 1969, 4 , 3611
34
also in accord with the expectations of ligand field theory.* The interpretation of the high ionisation energy regions of the metal carbonyl u.v.-p.e. spectra is much facilitated by a comparison with the spectrum of free carbon monoxide. The spectra of the simple PF, complexes. Ni(PF,), and Pt(PF,),, have also (e.g. Figure 14). Again close comparison with the spectrum been reported"."
15.91
u ,
20
18
16
14
12
10
15.83
20
18 1 6 14 12 IONI AT I0N E NE RGY Z
1 0
Figure 16 The He' p.r. spectru q1' PF, and Ni(PF,), (Reproduced by permission from Chem. Comm.. 1970. 1 12 1 )
of the free ligand proves highly informative. and Green et ~ 1 1 . ~ conclude from a " comparative study of Ni(CO), and Ni(PF,), that PF, is indeed more synergict than CO in keeping with chemical intuition. These authors also conclude that the metal d" shell. markedly split into its r z and e components in Ni(PF,),. is only slightly split in the platinum compound. This conclusion has been challenged by Hillier et crl. who interpret the Pt(PF,), He' spectrum of Lloyd and
* However, it is important t o remember that the SCF M O energies are not in general simply reiated to ligand field orbital energies (which d o not contain contributions from electron repulsion within the perturbed d shell). + Some readers might prefer the term rfec'rr,/nrRmtir.r.
e VClL
TI CI4
16 14 12 10 Figure 17 The He p.e. spectrum ofVCl, compared with that of TiCl, (Reproduced by permission from Chem. Pliys. Letters, 1970,7,414)
36
co-workers in terms of a much larger r2-c energy separation than that observed in the nickel analogue. Turner er a/.' have also published the He' p.e. spectra of some biscyclopentadienyl (sandwich) complexes, namely those of Fe, Cr, Co. Ni, and Mg. The sequence, n > CT > n, now firmly established for the highest occupied MOs of benzene,122are confirmed to hold in the planar C,H, group also. It has been commonly assumed in the past that the highest occupied MOs of transition-metal complexes are those largely localised on the metal atom. This notion is neatly confirmed by the u.v.-p.e. spectra of the simple carbonyls discussed above, and also by a comparison of the spectra99 of VCl, and TiC1, (Figure 17). These two spectra are ver! similar in general appearance, but that of VCl, shows in particular an additional band at low ionisation energy : this, without doubt. must be due to the single unpaired d-electron (probably occupying an anti-bonding e MO). The spectrum of ferrocene,' when compared with that of (n-C,H,),Mg, also clearly shows that the metal d-electrons ionise at lower energy than the electrons largely localised on the cyclopentadienyl rings. However. it is not generally true that the metal d-electrons are the least strongly bound in transition-metal compounds. For example. Evans er al. have shown that the first p.e. band in the pentacarbonylmanganese halides, (CO),MnX, is due to ionisation of the essentially 'lone-pair' halogen electron^.'^^ The u.v.-p.e. spectrum of Fe(hfa), also suggests that the ligand ionisations may precede the d ionisations (though it is possible here that the first ligand and d ionisations occur at very similar energies). The spectrum of nickelocene, (n-C,H,),Ni,' is also intelligible only if some overlap of the manifolds of ligand levels and dlevels is invoked.
3 X-Ray Photoelectron Spectroscopy

The technique of X-p.e. spectroscopy (ESCA)is less well established than vapourphase u.v.-p.e. spectroscopy, although the principles underlying the measurements have been known for many years. Only with the advent of electron analysers ofhigh inherent dispersive power was it realised that core ionisations led to narrow photoelectron bands with an inherent width governed only by the uncertainty principle. The experimental problems remained considerable, however, and a formidable effort on the part of the Uppsala was necessary before the measurement of X-p.e. spectra became relatively routine. The information obtained from X-p.e. studies is novel, but difficult to assess, especially as regards work on solid samples. Comparatively few papers have appeared on the subject. most authors choosing to calibrate their spectra by reference to the earlier work of Siegbahn er 01. However, disturbing discrepancies are apparent between ionisation energy data published at different times by the Swedish workers. Indeed it is the opinion of the present reporters (for reasons
153
154
S. Evans, J . C. Green, M . L. H . Green, A. F. Orchard, and D. W. Turner, Discuss. Faraday Sor., 1969, 47, 1 12. 'Alpha, Beta, and Gamma Ray Spectroscopy,' ed. K. Siegbahn, North Holland, Amsterdam, 1965.
37
discussed in detail below) that it is hardly meaningful at present to quote absolute values for core binding energies. Nor is there likely to be much profit in the close comparison of ionisation energy data reported by different groups, especially when sample preparation methods have not been standardised. A number of reviews have appeared during 1970,4*'55-158 including the published version of Siegbahn's lecture at the 1969 Royal Society sympo~ium,~ l ~ ~ and an article by Delgass et ~ 4 1 . discussing the possible applications of X-p.e. spectroscopy to problems in catalysis. The important point is made in the latter work that a considerably improved vacuum is essential if meaningful results are to be obtained in this area. The ESCA literature proves less amenable to a compilation of investigations of the kind provided in the previous section on u.v.-p.e. spectroscopy, since many authors quote limited data for an extremely large number of compounds. The list in Section 3C is not therefore intended to be comprehensive in such cases : only representative information is included. The reporters felt that an adequate review of the 1970 publications would be impossible without some reference to earlier work, especially to the most valuable monograph on gas-phase X-p.e. spectroscopy by Siegbahn et aL3 which appeared in November 1969. Without such references too much of the work reported in 1970 would lose its true context. Instrumental problems in solid-state and gas-phase ESCA work are considered first, the discussion concentrating on experimental difficulties that are distinct from those that arise in u.v.-p.e. spectroscopy. The central problem of calibration is then examined, attention being drawn to the uncertainties in solid-state measurements. A review of the more significant results is preceded by a section concerned with satellite lines in X-p.e. spectra, this structure being of widespread occurrence and a possible source of much confusion; X-p.e. studies of the valence regions of metallic and non-metallic elements are considered subsequently, and this section is followed by a discussion of the origin and meaning of the 'chemical shifts' observed in core binding energies. A. Experimental Methods.-The general theory of high-energy electron analysis was described by Siegbahn in 1965.'54 There are essentially two methods: one may employ electrostatic deflection analysis as is now usual in u.v.-p.e. spectroscopy, or one may analyse using magnetic deflection. The latter technique, being somewhat unsuitable for low electron kinetic energies, has been relatively little used in u.v.-p.e. work, though Turner and May'59 have described a ~ also Fadley et al. at successful equipment. Both Siegbahn rt al. at U p p ~ a l and~ Berkeley' have built double-focusing magnetic analysers of considerable size. The constructional material must be iron-free and the analysers extensively screened from stray magnetic fields. A current supply of great stability is essential ;
55
156
"
'
159
W. N . Delgass, T. R. Hughes, and C. S. Fadley, Catalysis Rev., 1970, 4, 179. R. Nordberg, Adv. X-Ray Analysis 1970,13, 390. K . Siegbahn, Ann. Physique, 1968, 3, 23 1. J. M. Hollaader and W. L. Jolly, Accounts Chem. Res., 1970, 3, 193. D. W. Turner and D. P. May, J . Chem. Phys., 1966, 51,471.
38
the Berkeley group have experienced considerable difficulty in converting current readings into electron kinetic energies and frequently quote only the former on their spectra. j 5 A11 commercially available X-p.e. spectrometers, however, incorporate electrostatic deflection analysers. which are simpler to operate and appear to give results comparable with those obtained from magnetic deflection instruments. The general features of the three established commercial machines have been briefly reviewed by Brundle. Considerable interest has also been aroused by a recent addition to the market* which incorporates several novel features designed to improve resolution without great sacrifice in sensitivity, including a dispersion compensation system originally suggested by Siegbahn et a/. to circumvent the large inherent width of the exciting X-ray lines. Monochromatisation of the X-radiation will result in a substantial reduction in photon flux, and a concomitant decrease in electron count rate. The Siegbahn design makes use of a dispersing crystal as shown in Figure 18 : a lens (not shown in the Figure)
X- R AY
C RY STA L
TARGET
SOURCE
ELECTRON SPECTROMETER
DETECTOR
Figure 18 A diagram illustrating the principle of combined crvstnl and magnetic focusing .for eliminating inherent width of X-radiation. The part o f the instrument labelled electron spectrometer includes both a lens and an ann1.vser system
(Reproduced by permission from Electron Spectroscopy for Chemical Analysis, Nova Acta Regiae Societatis Scientorum, Upsaliensis, 1967) focuses electrons from different points on the sample surface onto an array of electron multipliers, yielding an overall image of spectrum, thus enabling the full intensity of the X-ray source to be utilised whilst reducing its effective linewidth to a level determined by the aberrations of the analysing system. .Y-Ray photoelectron spectroscopy is essentially a surface technique. Experiments on iodostearic acid and on silver have shown that the mean * A spectrometer from Hewlett-Packard.
39
escape depth for electrons of several hundred eV kinetic energy is only of the order of tens of angstroms. Surface contamination is therefore a most worrying problem. Having pumped on the sample, the surface may of course be 'cleaned' (usually with an ion-gun), but it should be remembered that, even at a pressure of l o p 9torr, the sample will become coated with a monolayer of residual gas in a matter of minutes : only very brief scans of the X-p.e. spectrum may therefore be possible before contamination produces serious interference. The use of pressures considerably higher than torr is fairly common and in such cases very great care is necessary in the detailed interpretation of results. Radiation damage to the sample is rarely a serious problem with the relatively soft MgKa and AlKa radiation normally used, but there may well be difficulties when the harder Cu and Mo sources are employed. Sample damage has been noted when Auger spectra are excited by high-energy electrons.2 The photoelectrons are now routinely detected by means of channel electron multipliers. Geiger tubes were originally employed,2 but these suffered the disadvantage that the electrons had to be substantially accelerated in order to penetrate the tube windows : moreover, these windows were extremely thin and very fragile. The response time of the Geiger tube was also rather long, and the background signal large. The main drawback of the channel electron multiplier is its high cost, but Nilsson et ~ 1 . ' ~ ' have described a relatively inexpensive alternative design worth particular consideration if a bank of such multipliers is contemplated. Since only very low electron count rates are frequently obtained, rather sophisticated data-handling facilities are often necessary (this is especially true of gas-phase X-p.e. spectroscopy). The Siegbahn group employ a step plotting method with the use of multichannel ana1yse1-s.~~~ Vapour-phase X-p.e. measurements have proved extremely difficult, principally for the following reasons. In the first place, the count rate is inconveniently low, often just three or four counts per second, so that spectra take a considerable time to run. This in turn raises the problem of maintaining the gas pressure reasonably constant during the long scan, and highly expensive counting equipment is required. The deleterious effect of sample vapour on the pumping system and in particular on the target area, well known in u.v.-p.e. spectroscopy, can be very serious in X-p.e. work because of the more stringent requirements of equipotential surfaces. A further complicating factor is the variation of ionisation energies with gas pressure, though some disagreement exists in the literature with regard to the importance of this effect. Siegbahn et aL3 consider a variation of 'several eV' over a pressure range of two orders of magnitude to be quite normal, but ThomasI6' finds no evidence for such large pressure shifts, quoting only a difference of 'less than 0.1 eV'. However, it seems reasonable to suppose that the data obtained by extrapolation to zero pressure are more reliable than the results of measurements at just one pressure. Ionisation cross-sections are also dependent on sample pressure, increasing with pressure up to about 0.15 torr
160
16'
0. Nilsson, L. Hasselgren, K . Siegbahn, J. Berg, L. P. Andersson, and P. A . Tove, Nuclear Instr. Methods, 1970, 84, 301. T. D. Thomas, J . Chem. Phys., 1970, 52, 1373.
40
but then decreasing as a result of self-absorption of photoelectrons by the gas molecule^.^ It should be noted that both pressure-induced effects, the variation in ionisation cross-section and the binding energy shifts, are usually different for distinct ionisation processes in the same molecular species. Several suggestions have been put forward with regard to the investigation of low intensity processes. These include the design of an improved X-ray source with a high-power electron gun and incorporating a water-cooled, rotating anode, and also proposals for the minimisation of analyser aberrations. There is in addition the use of detector arrays instead of the usual single ~ h a n n e l t r o n . ~ Siegbahn er a/. have also suggested the use of a 'cut-down' process to secure improvement in resolution.' Highly efficient data-processing equipment is also obviously of major importance. In solid-state work the sample may be prepared in a number of ways. The simplest method is to grind the material to a fine powder which is then spread on adhesive tape (this ideally should be electrically conducting but rarely is). A more controlled procedure possible with volatile materials is condensation onto a cryo-tip: this permits the deposition of uniform layers of variable thickness. A method which has been developed with biological studies in mind utilises frozen solutions.'" In the case of aqueous solutions, for example, the oxygen Is bands of the solute are of course 'swamped' by those of the solvent so the solution has to be rather concentrated. Other techniques of sample preparation that have been described include 'electrospraying'2 and 'molecular plating'. ' 6 3
The Calibration Problem. Critical concern for certain ambiguities in the basic X-p.e. measurement has been noticeably lacking, especially among users of the commercial instruments. It can be seen from Figure 19 that for a metallic sample in electrical contact with the spectrometer the interpretation is fairly straightforward. The electron kinetic energies are measured relative to the common Fermi level of sample and the metal from which the spectrometer is constructed. But the situation is more than a little confused in the case of nonconducting samples. The concept of a Fermi level is, to say the least, ill-defined for such materials and the practice of hopefully locating this level midway between the top of the valence band and the bottom of the conduction band leaves much to be desired. To avoid surface charging effects (see below), the sample layer should clearly be as thin as possible and deposited on a suitable electrically conducting material: if the layer of sample is sufficiently thin the supporting medium may also provide convenient reference lines. Electrical conduction in such circumstances will occur by some kind of 'hopping' mechanism. It must always be recognised, of course. that very thin films will have properties differing from those of the tnaterial in bulk, and further careful investigation of this point is necessary.*
lh2
163
L. N. Kramer and M . P. Klein, J . Chem. Phys., 1969, 51, 3620. G. Malmsten, 0. Nilsson, I . Thoren, and J . E. Bergmark, Physica Scripra, 1970,
1. 37.
* There is the more general point that, even when a single crystal is studied, for example,
the X-p.e. technique may never yield data truly representative of the bulk material.
41
A more profound analysis of the problems involved in the calibration of the X-p.e. spectra of semiconductors has been given by Langer and V e ~ e l y who '~~ performed a variety of experiments in an attempt to elucidate the nature of the energy shifts obtained for a solid sample in various physical states. These experiments paralleled the work of Nordberg et ~ 1 . 'Both groups found substantial ~ ~ variations in 'absolute' binding energies. Nordberg et al. observed a shift of
X - RAY
TUBE
DETECTOR
I I
1
I t
1
S P E C IHE N
E L E C f R O N S P E C 1 R O M E TER
Figure 19 A diagram showing the derication of binding energies from solid-state X-p.e. data. The specimen is assumed to be in electrical contact with the spectrometer (Reproduced by permission from 'Electron Spectroscopy for Chemical Analysis,' Nova Acta Regiae Societatis Scientorum, Upsaliensis, 1967)
164 165
D. W. Langer and C. J. Vesely, Ph-vs. Reu. ( B ) , 1970, 2, 4885. R. Nordberg, H . Brecht, R. G . Albridge, A. Fahlman, and J. R. van Wazer, Znorg.
Chem., 1970,9,2469.
42
Electronic Structure and Magnetism of Inorganic Coinpounds
several eV on grinding the sample with graphite and Langer and Vesely encountered effects of similar magnitude on binding a single crystal of ZnS with a fine copper mesh or on coating the sample with a thin layer of carbon black. The latter workers were also surprised to find no significant shift in ionisation energy on varying the intensity of the exciting S-radiation. differential surface charging effects having been anticipated. Calibrant materials other than graphite have been studied. Siegbahn et appear to favour pump oil. Even with the most efficiently trapped oil pumps it seems impossible to prevent some quantity of oil streaming back into the target region (and. incidentally. even as far as the electron multiplier),'60 and forming a layer on the surface of the sample. Only by use of turbomolecular pumps can this apparently be avoided. The exact constitution of the oil layer is usually uncertain, for a variety of reasons. and other hydrocarbon contaminants (from O-ring seals, vtc.) may be expected to find their way to the target area. All things considered, this method of calibration is not without its risks.* Even the very considerable experience of the Uppsala group of calibration with hydrocarbon surface deposits has not been proof against error : many of the figures quoted in the famous 1967 monograph of Siegbahn et ~11.' for sulphur core electron binding energies in a variety of compounds were radically revised in a subsequent paper.16' The later results are also in serious disagreement with data reported by Kramer and Klein l h 7 despite the fact that these workers calibrated their spectrometer by reference to the pioneering work of Siegbahn tv ~ i 1 . l It is probable that the contaminant hydrocarbons have a significant effect on surface charging. which may explain the discrepancy noted between the phosphorus 3 p binding energy in triphenylphosphine reported by Pelavin et al., 1 6 8 who use the hydrocarbon as calibrant. and the figure quoted by Blackburn ti( t 1 1 . . ' ~ ' who calibrate by reference to the carbon Is binding energy in the compound itself. This practice of 'internal calibration' is clearly problematical. True, it is known that the carbon I s binding energy is comparatively insensitive to chemical environment in certain types of compound. but there remains a risk in assuming that it will necessarily be the same in, for example, Ph3P0 and Ph,P. The calibration of gas-phase S p.e. spectra is much less of a problem. Siegbahn t't ( 1 1 . ~ have discussed the question in some detail, and provide many examples. The problem has also been investigated by T h ~ m a s . ' ~ ~ ~ ' 'The " ' ~ ~ primary
Ih6
''Ih8
'"
"'
'"
B. J. Linberg. K . Hamrin. G . Johansson. U . Gelius. A . Fahlman, C. Nordling, a n d K. Siegbahn, Physica Scrrpra 1970. 1. 286. L. N . Kramer and M . P. Klein. J . Chem. Phj9s.. 1969, 51, 3618. M. Pelavin, D. N . Hendrickson, J . M . Hollander, a n d W. L. Jolly, J . Phys. C h ~ r n . , 1970, 74, 1 1 16. J . R . Blackburn. R . Nordberg, F. Stevie, R . G. Albridge. and M. M . Jones, Znorg. Chem., 1970. 9. 2374. T . D. Thomas. J . Arnrr. Chrrn. Soc.. 1970. 92. 4184. T. D. Thomas. J . Chrtn. Phjms.. 1970. 53. 1744.
* The method - 1 1 1 . in a n ) case. o n occasions be bedevilled by failure to detect the hydrocarbon contaminant lint. ' '"
43
calibrants, as in u.v.-p.e. spectroscopy, are the inert gases (neon, argon, krypton, and xenon) but the procedure required is less straightforward : since pressuredependent effects are possibly more important than in u.v.--p.e.work, extrapolation to zero pressure is necessary. A series of secondary calibrants may be established by reference to the inert gases but, where p.e. bands are calibrated from inert gas lines relatively remote in energy, assumptions concerning the linearity of the analysing system must always be carefully evaluated. A suitable choice of secondary calibrant will often permit the highly accurate measurement of binding energies in a compound relative to the selected reference gas, but the absolute reliability of the data will depend on the commonly much less accurate original calibration. The other fundamental problem limiting the accuracy of ionisation energy data arises from pressure-dependent phenomena. These difficulties can only be partly eliminated by simultaneously feeding the calibrant gas and the vapour of the compound under investigation into the spectrometer, but this is always a desirable practice. The internal consistency of a calibration may often be checked by examining the co-excited Auger lines in the X-p.e. spectrum. An extensive compilation of solid-state Auger energy data has been produced by Siegbahn et d 2The Auger to help calibrate the X-p.e. spectrum of copper was used by Malmsten et spectrum of molecular plated promethium metal, and Langer and V e ~ e l y ~ ~ used zinc Auger data in their work on the zinc chalcogenides. But Auger structure cannot be used as a primary means of calibration, mainly because of the quite different modes of excitation employed in X-p.e. spectroscopy and in Auger spectroscopy. The binding energy Efh of a particular electronic shell relative to the Fermi level of the specimen is given by2
Er, = hv
-
4sp- Ekin
where v is the frequency of the incident X-radiation, &in the measured kinetic energy of the photoelectrons, and 4hSp the work function of the spectrometer material* ( c j Figure 19). The crucial unknown quantity is 4sp, determination the of which requires standard reference compounds with known Efb values. Using just one E i figure, measurements may be made with various X-ray sources, when a plot of Ekin against photon energy, hv, will easily give $sp. Such methods are used extensively, the necessary Ek data being taken from the work of Siegbahn et aL2 However, if the published work on sulphur 2 p ionisation is any indication, the data available in the 1967 monograph are by no means entirely reliable, so that little absolute significance can be attached to results based on such a calibration. It is usually assumed that the work function of the spectrometer remains constant over a decent interval of time, and this is probably true in solid-state work (though clearly a spectrometer should be re-calibrated frequently, especially if it has been employed partly for gas-phase X-p.e. studies).
* & s p is frequently referred to as the work function of the spectrometer, and in practice is a parameter of the inetrument incorporating a number of undefined effects.
44
Surface-charging and other Eflects. The ionisation of semiconductors or insulating materials in the X-p.e. experiment usually results in the surface of the specimen developing a positive charge and therefore a positive potential with respect to the spectrometer. In the case of volatile samples these surface-charging effects can be investigated by examining layers of increasing thickness deposited on the specimen probe, and measuring the successive shifts in the apparent core ionisation energies. These shifts are often substantial and there is no reason to suppose that surface charging will influence different ionisation processes to the same extent. The effects appear to involve some kind of rapid equilibrium process since they are not very dependent on the intensity of the exciting X-radiation. 164 The phenomenon is not well understood theoretically but it seems that, experimentally, the best course of action is to reduce surfpe charging by the use of thin sample films or by grinding the sample with some highly conducting material such as graphite. Such effects will be strongly modified by contamination of the surface. But the influence of surface contamination on charging and other phenomena is very difficult to assess in detail. Impurities on the sample surface can affect the X-p.e. spectrum in many ways, including (i) the probability of Discrete Energy Loss (DEL) processes, which may lead to satellite bands, can be substantially increased (DEL effects are discussed below) (ii) bands characteristic of the contaminant may appear strongly in the spectrum (and cause particular confusion if the impurity and sample contain the same element) (iii) gas adsorption may significantly alter the electronic structure of the sample. especially the outer, valence shells (scrupulously clean surfaces seem absolutely essential for the reliable investigation of ionisation processes in the valence region).
B. Additional Structure in X-P.E. Spectra.--Auger Lii~es.'.~ Auger structure arises from radiationless transitions within the sample and is easily distinguished from the direct ionisation structure by the invariance of its position with the energy of the exciting X-radiation. As illustrated by the X-p.e. spectrum of CF,, reproduced in Figure 20, Auger bands are often of considerable intensity though they are rarely well resolved. Higher resolution Auger spectra may be obtained by excitation with a monochromatic electron beam, as shown in Figure 21. Two types of Auger transition may be distinguished : (i) a low-lying vacancy created by X-irradiation is filled by the transition of an electron from a higher shell, causing the radiationless ejection of a second higher shell electron (ii) a low kinetic energy electron originates from the shell having the primary vacancy. These are referred to as Coster-Kronig transitions, and are probably responsible for the considerable broadening that is evident in the p.e. bands arising from ionisation of valence or 'sub-valence' orbitals of predominantly s character. This effect is also illustrated by the CF, spectrum in Figure 20.
45
FLUORINE K AUGER
Cls
L
A '
555
560
""
6LO
650
"
950
955
" ' "
1110
I210
1110
1260
+ i
KINETIC ENERGY
695
690'
A 3d5 360 BlNOlNG ENERGY
i0
'
LO
i0
i0
I*
Figure 20 The ESCA spectrum of gaseous CF4 showing the valence region and the associated .fluorine KLL Auger (Reproduced by permission from 'ESCA Applied to Free Molecules,' North Holland, Amsterdam, 1969)
KINETIC ENERGY
Figure 21 Thefluorine KLL Auger spectrum excited by elecfron impact on gaseous C F , (Reproduced by permission from 'ESCA Applied to Free Molecules,' North Holland, Amsterdam, 1969)
46
Auger spectra have been used as an aid to calibration in some X-p.e. investig a t i o n ~ . ~ but in ~ ~ . ~ general they are more difficult to interpret than X-p.e. spectra and there are not expected to be any readily explicable chemical shift phenomena.
Str-itctlrrr dirr to .4dditionul Lines it1 the Esciting Radicition. Secondary structure in S p e . spectra is often due to impuritj lines in the source radiation. These additional lines maj arise essentially in two ways:
(i) The anode material in the X-ray source may contain impurities. A simple example. in the case of metallic anodes. is provided by the X-p.e. spectrum of H,S excited bj M g K r radiation [Figure 22(a)].3 Pronounced structure observed at very low ionisation energy was understood only when it was recognised that the magnesium anode material contained aluminium as an impurity :
-300
CK < 0
-200
z 0
U
2G2C
P
- 100
- -
1a,
-)
300
Ji
-__
el
5:3
533
LO
(b)
30
I , 20 lo
BINDING ENERGY
47
q 2 0 0s
1000
2 oc
0
I -
z 3
ioo
Figure 22 X-p.e. spectra of (a)gaseous H,S ( b ) water vapour and (c) ice to illustrate (i) cross-section differences between second and first row elements in the valence region (ii) the profound modijcation of the valence region in the solid state (Reproduced by permission from ESCA Applied to Free Molecules,North Holland, Amsterdam, 1969)
the band is in fact due to ionisation of the sulphur 2s shell by AlKa radiation.* (ii) Satellite lines may be present in the source radiation even when the anode material is absolutely pure, as a result of secondary transitions. The principal lines obtained from A1 or Mg anodes, the Kalaz radiation, arise from the 2S-2P transition in which a 2 p electron falls into a vacant 1s hole produced by electron impact. The emitted X-radiation has a substantial linewidth and an asymmetric intensity profile, mainly as a result of spin-orbit interactions in the * P state (leading to the a1 and a2 components). Satellite lines appear when, for example, the X-ray emission processes occur in the doubly ionised atoms. Their effects are nicely illustrated by the X-p.e. spectrum of neon gas3 reproduced in Figure 23. The satellite structure due to the Ka,, a4 lines is
* There is a particular risk of confusion when non-metallic compounds are used as anode materials, and great care should be taken to ensure that contaminant lines are not present. Non-conducting anode materials are of course susceptible to surface-charging effects which may induce energy shifts in the output radiation. The difficulties can be minimised by the use of very thin films (as in the case of the specimen), but it is also clearly necessary to standardise the form and thickness of the film.
NEON Is
310
320
330
340
350 360 370
380
390 LOO
110
L20
130
KINETIC ENERGY
Figure 23 The ESCA spectrum of gaseous neon at 0.5 torr e.rcited by MgKa radiation. The bands to high kinetic energ?. of the rnuin peak at ca. 384 eV are caused by secondary lines in the source as indicated. The ban& on the ION. energy side m e assigned as,follows: ( i ) bands 2. 3. and 4 arise.front discrete energ?. loss ( D E L )processes (ii) bands 7--12 are caused bj. shake-up processes (iii) brind 1 is the MgKa,,, 'shadow' of band 2 while bands 5 and 6 are the corresponding .shtrdoic-sof bands 7 and 8 (Reproduced by permission from 'ESCA Applied to Free Molecules,' North Holland, Amsterdam. 1969)
clearly discernible on the high kinetic energy side of the main photoelectron band (0). together with further structure which is appropriately labelled. Satellite lines in the source radiation are quite well understood for A1 and Mg and pose no real problems : but in the case of heavier metals yielding harder radiation a great deal of work remains to be done. 'Shake-up' arid 'Sltake-oj* Processes. In addition to the primary processes of direct (one-electron)ionisation, there may occur to a significant extent secondary many-electron transitions. Again the X-p.e. spectrum of neon gas (Figure 23) provides an excellent example, on this occasion attention being directed at the structure on the low kinetic energy side of the main p.e. band. The additional lines are largely due to compound processes of the type
( I ) Ne( ls23s22ph)--* Ne'( ls2s22p'3p) ( i i ) Ne(ls'2sZ2p6) ---* Ne2 '(lsZs2Zp5)
shake-up shake-off
Such transitions are forbidden in the orbital approximation, but their occurrence is fairly easily understood when configuration interaction is properly included in the description of the many electron states involved. Calculations of this kind have been performed by Siegbahn et aL3 to interpret bands 7-12 in the Ne X-p.e. spectrum, and the results are highly encouraging.
49
The appearance of shake-up lines clearly has relevance to a major problem in the interpretation of X-p.e. binding energy data - namely whether the ionisation processes are sudden or adiabatic. There is considerable controversy with regard to this problem, which hinges on the magnitude of orbital relaxation effects. The large number of quite inadequate calculations that have been reported serve only to confuse the issue. One group of authors, in connection with the 1s core ionisations of carbon monoxide, has concluded that the C 1s ionisation is adiabatic while ionisation of the 0 Is shell is sudden.* A configuration interaction approach implicitly assumes that the ionisation process is adiabatic, but an alternative theory proposed recently by Krause et is based initially on the sudden approximation. The theory postulates the instantaneous creation of a positive hole, and the resultant change in electric potential is used, in conjunction with time-dependent perturbation theory, to calculate the probability of shake-off occurring. The theory can clearly be extended to explain shake-up satellite structure, but fails to give a satisfactory account of why the energy of the outgoing core electron is affected by these secondary processes. The intensities of these satellite lines relative to that of the main peak is clearly a property of the molecule, and the effects are not pressure dependent. The observation of such processes in the solid state has not been reported, though there is no very obvious reason why they should not take place. The higher density of excited states may however lead to rather indistinct structure.
~ 1 . ~ ~ 9 ~ ~
Discrete Energy Loss (DEL) Processes. The three types of process considered above can occur to the same extent in both gases and solids, but DEL processes vary with the physical state of the sample. A nice example of a DEL process in the gas phase is provided by the bands 2 and 3 in the neon spectrum (Figure 23). The Ne 1s electrons, excited by the MgKa radiation, can induce transitions in neutral neon atoms through inelastic collisions. Thus
Ne(ls22s22p6)S-+ N e ( l s 2 ~ ~ 2 p ~ ) ~ S p-wave electron e e
+ Ne(ls22s22p6)lS + e* + Ne(ls22s22p53s)Por Ne(ls22s22p53d)P
The selection rules appear to be the same as in optical absorption, i.e. AL = 1 and AS = 0. Clearly the relative probability of DEL processes in gases must be pressure dependent. For neon gas at about 0.5 torr the 2p --+3s transition has a height about 5 % that of the major peak. DEL processes in metals are fairly well understood. The most common type are termed plasmon loss and arise when the creation of a positive hole causes the electron cloud to oscillate.73 Because of the long range nature of the Coulomb forces such oscillations may extend through a considerable part of the crystal and the outgoing electron may lose energy to the oscillating electron gas in units of hw,. The situation is illustrated by the spectrum of liquid indium,
I. H. Hillier, V. R. Saunders, and M. H. Wood, Chem. Phys. Letters, 1970, 7 , 323.

J. M. Ziman, Electrons and Phonons, Clarendon Press, Oxford, 1960.
50
Figure 24 The ESCA spectrum of'tlie indiirrn 4d region showing ttvo satellite peaks caused by plasmon loss processes (Reproduced by permission from Pli!sica Scripta. 1970, 1. 5 5 )
reproduced in Figure 24,'74,'7 5 where the two peaks arrowed are almost certainly plasmon loss peaks. Two types of plasmon may be distinguished: volume plasmons of angular frequency wp and surface plasmons of angular frequency us. From the continuity relations we have"6
w, =
li_ \'l E
UP
where E i s the dielectric constant of the medium above the metal. For a vacuum, and a scrupulously clean surface.
w w =p
\,5
In this case the probability of surface plasmon excitation is negligible compared to volume plasmon interaction. However, if the surface is contaminated with oxide ( E > I ) the probability of DEL processes through surface plasmon loss dramatically increases' and the frequency drops. For non-metals the theory is considerably less well developed. Presumably electron-exciton interaction is possible but the magnitude is wholly u n k n 0 ~ n . IThe type of ~~ DEL process found for neon may also be significant, though the main band may be too broad for such effects to be observed. Electron-phonon i n t e r a ~ t i o n is~ ~ '
7 4 9 1 7 5
Y . Baer, P. F. Heden, J . Hedman, M. Klasson, C. Nordling, and K . Siegbahn, Solid

Stare Comm., 1970, 8 , 517.
Y. Baer, P. F. Heden, J. Hedman, M . Klasson, C. Nordling, and K. Siegbahn, Physica

Srripta, 1970, 1, 5 5 .
H . Raether in 'Springer Tracts in Modern Physics no. 38', Springer-Verlag, Berlin, 1965. A S . DaLydov, 'Theory of Molecular Excitons.' McGraw Hill, New York, 1962.
51
best treated using the formalism of second-quantisation. Although creation and annihilation of phonons is common the energy changes involved are minute, far smaller than the inherent linewidth so that, unless angular distribution is considered, the effect may be negligible. Electron-electron scattering' 7 3 in metals will involve the interaction of electrons with widely differing k values.* These are spread over a large energy range and probably contribute a general asymmetric background rather than discrete peaks. The electrons may be diffracted by the crystal lattice. Inelastic collisions with individual atoms probably lead to scattering but the diffraction will lead to a pronounced angular dependence of the electron flux. The theories are at present ill understood and unwieldy but some experimental work has been done. C. Compilation of References (i) Gus Phase N,(N l ~ ) ; ~ *02(0~ ) ; ~ , NO(N Is, 0 1s);3,179 '~* l '~* CO(C Is, 0 1s);3,171*178 H,O(O is);, H2S(S2 ~ ) ; ~ C02(C Is, 0 ls);3,178CS,(C Is, S 2 ~ ) ; ~ N,O(N Is, 0 ~ s ) ; ~ T '0~ * N Is, 0 ls);, S02(S2p, 0 ls);, HCN(C Is, N ls).'?* N 2( Carbon-containing molecules : C 1s measurements. Where core binding energies for other elements in the molecule are reported, this is indicated. CF4I7*( F ~ s ) ; ~ ~ ~ ~ ' C C I , ( + C12p);17' CBr4(+ Br MeF17',17*(+ F iS);3 ( c 1 MeCl(+ C12p);'70MeBr'70(+ Br3d);3CHF,'78(+ F ~ s ) ; ~ , ' ~ ~ ~ '3~ ' C H C ~ 2p);170 CHBr,(+ Br 3d);3 CH2Cl,(+ C1 @;7 )I' CH,Br,(+ Br 3 d ) ; 3 CH4;,,16, ; C2H, ;3,163,170 n-propane;, C2H4;163,178 C2H2 1 6 3 , 1 7 8 benzene ;3,163 cyclo; ~ HCOOH hexane;16, neo-~entane;'~, MeCHO(+ 0 1 ~ ) MeOH( + 0 ls);33178 ( + 0 ls);17* c y ~ l o p r o p a n e ; ' ~ MeCO,H(+ 0 ~ Me,CO(+ 0 1 ~ ) ; ~ MeCH,OH(+ 0 lsj;, MeC02CH,Me.3 Nitrogen-containing molecules : N 1 s measurements. ONF, , NF, , N2F4, ONCl, N2H4;179NH3;39'79 MeNH,, Me,NH, Me,N;'79 PhNH,, PhN0,.3 Fluorine-containing molecules : F 1 s measurements. SF,( + S 2p), SOF,
(+
s 2p).3
Xenon-containing molecules : Xe 3d measurements. XeF, , XeF,, XeF,, XeOF,., The gas-phase ESCA spectra of the inert gases are also given in reference 3. (ii) Solid State Detailed Individual Studies 1. The following metals in the valence and core regions : indium, silver, iron, osmium, cobalt, iridium, nickel, platinum. copper, gold, ruthenium, rhodium, palladium. 2. The valence and core regions of the isoelectronic series LiF, BeO, BN, graphite."'
1743175
D. W. Davis, J. M. Hollander, D. A. Shirley, and T. D. Thomas, J. Chem. Phys., 1970,

52, 3295.
179
18*
P. Finn, R. K. Pearson, J. M. Hollander, and W. L. Jolly, Inorg. Chrm., 1971, 10, 378. K. Hamrin, G. Johansson, U. Gelius, C. Nordling, and K. Siegbahn, Physica Scripfa,
1970, 1, 277.
* k is the electron wave vector.
52
3. The following semiconductors: ZnO, ZnS. ZnSe, ZnTe;"" VC,, NbC,, TaC ,. 3. The following phosphine derivatives : Ph3P and Ph,PO, Ni(Ph,P),CI,, Pd(Ph,P),C12. Cd(Ph,P),CI, . I o 9 5. Other compounds: polywater : I e z SnC1,,2(NH2COCH=CH,);'83 CuOA1,0, : l 8 4 promethium (molecular-plated). 1 6 3 Chemical Shift Investigations Sulphur (2p},'66~'6'~'8s range from Na,S 162.0 to SOF, 170.2eV; examples:
0
PhCH,SSCH,Ph. 163.3: PhCH2SSCH,Ph. 163.9 and 166.1 : PhCH,SSCH,Ph,
II
0
164 1 and 168.2: Na,S20, 167.2eV
II
I1
rangefromNaNO34O7.4toCrN 396.6eV;exarnples:(NPCl2), , Nitrogen( ls).lq8 399.5; Rh(NH,),(NO,),. 407.3 and 400.7; NaNO,, 404.1; Co(NH,),(NO,)CI,, 404.0 and 400.0: S,N,. 402.1 : P,N5. 397.8 eV.
Phosphorus ( 2 p ) . l 6 * range from NH,PF, 137.3 to CrP 128.8 e V ; examples: (NPCI,), , 134.5: red phosphorus, 130.1: K P F , 0 2 , 134.8 : Na,P,O,, 133.3; BP. 129.5: PBr, . 138.4eV. Iron (3p).16' range from iron metal 52.4 to K,FeO, 57.7eV; examples: ferrocene. 53.7: FeSO,. 55.2: I-e2(S0,),.sH,0, 57.0: K,FeF,, 57.7 eV. Boron (ls),lg6range from NaBF, 195.1 to B,C 186.7 eV; examples: H,BO,, 193.2; Na,B,O,, 192.2: BN, 190.2: Na2B,0,,10H20, 192.8; C2B9H,l,C,H,N, 188.4; NaBPh,, 187.7 eV. Chromium ( 3 p ) , l S 6 range from K,Cr,O, 48.7 to CrN 43.2eV; examples: Na2Cr0,,4H,0, 47.9 : Cr(H,O),(NO,), .3H,O, 45.4; K,Cr(CN),, 44.8 ; K,Cr(CN),(NO), 44.8 ; Cr(NH,),Cl,. 44.7: Cr2(OAc),.2H,0, 44.5 eV. Silicon ( 2 ~ ) , range from Na,SiF, 107.4 to elemental Si 99eV; examples: '~~ (H2Si20,}.104.2: SIB,, 102.4; (SiS2).103.1 ; Zn2Si0,, 102.2eV. Carbon (ls).186-188 range 11.9eV from C'H,CH2NH2 to CF,; examples:
L. Rarnqvist, K . Harnrin, G. Johansson, U . Gelius, and C. Nordling, J . Phys. Chem.,
Solids, 1970, 31, 2669.
'"
I84
la6
In-
I**
R . E. Davis, D. L. Rousseau, and R. D. Board, Scienrr, 1971, 171, 167. M. F. Farona, J. ti. tirasselli, H. Grissrnan and W . M . Ritchey, Znorg. C h r m . Acta, 1969, 3, 495. A . Wolberg, J . L. Ogilvie, and J . I-, R o t h , J. Cafalj~.si.s, 1970, 19, 86. B . J . Lindberg, K . Hamrin, G . Johansson, U . Gelius. A . Fahlman, C . Nordling, and K . Siegbahn, University of Uppsala, Institute of Physics, Report 638, 1970. D. N . Hendrickson, J. M. Hollander, and W. L. Jolly, Inorg. Chem., 1970, 9, 612. U. Gelius, P. F. Heden, J . Hedrnan, 8. J. Lindberg, R. Manne, R. Nordberg, C . Nordling, and K . Siegbahn, Physica Scripra, 1970, 2, 70. U. Gelius, P. F. Heden, J. Hedman, B. J. Lindberg. R. Manne, R. Nordberg, C . Nordling, and K . Siegbahn, University of Uppsala, Institute of Physics, Report 714,
1970.
53
shifts from CH,CH,NH, : (CH,),CO, 0.6; SH,COO-Na+, 0.3; cyclohexane, 0.4; CH,Br,, 2.3; CHCl,, 4.8; CF,COO--Na+,7.3; urea, 3.9eV. Platinum (4f),lS9range from (Ph,P),Pt(Ph,P), 71.7 to (Ph,P),PtCI, 73.7 eV.
D. General Discussion of Results- Valence Region Studies. These have been chiefly confined to gases and metals. For gases ESCA has greatly extended the original work of Compton and Allison in the thirties.'" Thus the s-orbital cross-section is found to be larger than that of p-orbitals in neon :3 this appears to be true of all first-row elements and is illustrated in the spectrum of CF,., However, in molecules containing second-row species the situation is reversed. Thus the argon spectrum shows greatly enhanced p-orbital ionisation crosssection3 and this is reflected in the spectra of H 2 0 and H,S reproduced in Figure 22., tho ma^'^' and also Siegbahn et a!., have used this differential s / p crosssection to calculate the atomic constitution of the molecular orbitals in CO. In addition it is the valence region which suffers the largest change on solidification of a vapour: the spectra from water vapour and ice are also compared in Figure 22. The considerable broadening and loss of structure in the solid state seems to be quite general. For metals the situation is more complex. For the material in bulk, the electron wavefunction may be written as a Bloch function'73
= uk(r) l k r P
where k is the electron wave vector. It can be shown, in the case of transitions induced by electromagnetic radiation, that for a Bloch function we must have
k'= k
+n +K
where k' is the final electron wave vector, n the photon wave vector and K a reciprocal lattice ~ e c t o r . ' ~This is the equation of k-conservation and will hold ' in the bulk material. On the surface, however,only the value ofk in the plane of the surface will be conserved since the value of k perpendicular to the surface is not defined. Thus the understanding of spectra obtained from metals depends on whether the process is primarily a bulk or surface effect. In the case of X-ray induced transitions it is probably reasonable to assume that the density of states in the very high energy region of k is sensibly continuous so that, even though only vertical transitions are permitted in the reduced zone scheme, the intensity pattern of the spectrum should reflect the density of states in the k region only. 1 7 5 The valence region of metals has also been examined by u.v.-p.e. spectrosc0PY19'-'97 and here without doubt the penetration depth cannot be more than
C. D. Cook, K. Y. Wan, U. Gelius, K . Hamrin, G. Johansson, E. Olson, H. Siegbahn, C. Nordling, and K . Siegbahn, University of Uppsala, Institute of Physics, Report 717, 1970. I g o A . H. Compton and S. K . Allison, 'A'-Rays in Theory and Experiment,' MacMillan, London, 1935. 1 9 ' N . V. Smith, Phys. Rev. Letters, 1969, 23, 1452. lY2 D. Brust, Phys. Rev. Letters, 1969, 23, 1232. 'y3 D. E. Eastman, J . Appl. Phys., 1969, 40, 1387. lY4 W. E. Spicer, Phys. Rev., 1967, 154, 3 8 5 . 19' C. N. Berglund and W. E. Spicer, Phys. Rev., 1964,136, A1030. 1 9 6 N. V. Smith, and W. E. Spicer, Phys. Rev. Letters, 1969, 23, 769. l 9 ' T. A . Calleott and A. U. Macrae, Phys. Rpv., 1969, 178, 966.
54
Electronic Structure and Magnetisnz of Inorganic Coinpounds
a few angstroms. Thus the surface must be scrupulously clean of oxide and hydrocarbon contaminants and the pressure low enough to ensure that it stays clean. This pressure is impossible to attain in the traditional u.v-p.e. spectrometer owing to diffusing helium from the lamp. which cannot be avoided even with the most efficient differential pumping. Possibly the only experimental arrangement which would generate meaningful results would be the use of synchroton radiation and turbomolecular pumps (to avoid oil contamination). The results obtained from u.v.--p.e. work on solids will be very difficult to interpret and considerable controversy exists in the literature. The intensity distribution in these spectra, however, is unlikely to represent in any simple way the density of states in the metal. Thus, until the major theoretical problems are settled. .Y-p.e. spectroscopy probably provides the more hopeful route to information on density of states especially as the reference Fermi level is well defined. A major paper by Baer er d.'"has explored the band structure of a number of metals and their general conclusions are : (i) there is a steady increase in the half-width of the valence band on going down a given transition-metal group (ii) discrete energy loss and scattering processes are much more important for metals with unfilled d-bands. Scattering occurs both for the valence and core levels and is correlated with the fact that. for these metals, the maximum of the valence band is very close to the Fcrmi surface (iii) metals of face-centred cubic structure are found generally to give broader bands (though of similar overall structure) to metals having a hexagonal closepacked structure ( i f . ) the noble metals. copper. silver. and gold, have the maximum in their valence band considerably removed from the Fermi surface. For these metals, scattering and discrete energy loss processes are quite unimportant ( 1 . ) the heavier metals such as iridium, platinum, and gold show two peaks in the band structure and rhodium shows an anomalous flattened structure of uncertain origin. The band structure of non-conducting materials is more difficult to interpret. Hamrin et 01.'~' have reported the band structure of the isoelectronic series LiF. BeO, BN, and graphite (see Figure 25). The bandwidth steadily increases from
55
BINDING ENERGY
CjLOS
I
cis
MgKa.,
I
Xcr' K c j u4
,50001
30
20
ElNDlNG ENERGY
Figure 25 The complete ESCA spectra of LiF, BeO, BN, and graphite showing especidy the increasing complexity of the valence region as the electronegativity difference diminishes (Reproduced by permission from Physica Scripta, 1970, 1, 277)
56
Electronic Strrrcture and Magnetism of Inorganic Compounds
LiF to graphite and shows increasingly complex structure. Thus there are two maxima in the band of BeO, three in BN. and four in graphite, though one of the latter maxima may be due to impurities. Little evidence of discrete energy loss processes was encountered. Langer and Vesely16' report the band structures of the zinc chalcogenides and compare them with various calculations. The best agreement is obtained with empirically refined OPW* results, though these contain certain constant errors. For the Zn 3d levels the calculated binding energy is always too high in the SC-OPW method when the Slater exchange approximation is used. The error may lie in this approximation or in the neglect of relaxation energy. Agreement with K K R t calculations was quite good, except in the case of the zinc oxides. The same authors also compare their results with optical reflection and electron energy loss data, which lend support to their assumption that the Fermi level lies midway between valence and conduction bands.
Figure 26 The ESCA spectrum in tlie.fiuorine Is region of a gaseous mixture of CF4 and MeF (Reproduced by permission from J . Amer. Chem. Soc., 1970. 92, 4184) * The Optimised Plane Wave method. + Korringa-Kohn-Rostoker theory.
57
Core Level Studies. The main interest in ESCA work to date has been in the relatively small but quite reproducible shifts in the binding energies of core levels in different compounds of the same element. In gas-phase work these shifts are illustrated by Figure 26,l7' which shows both MeF and CF, fluorine Is ionisations, and for solids by the spectrum of [Co(en),(NO,),](NO,) (Figure 27119* where the three chemically distinct nitrogens give rise to the triple N Is
356
404
$12
(EV)
aindlng
energy
Figure 27 The ESCA spectra of frans-[Co(NH,CH,CH2NH,),(N0,),I (NO,) in the nitrogen Is region showing how the three chemically distinct atom types are distinguished (Reproduced by permission from Inorg. Chem., 1969, 8, 2642)
peak. Sufficient has been said earlier about the inaccuracy of calibration methods in X-p.e. work, the doubtful position of the reference level in the non-conducting materials, and the possible effects of surface charging, to make comparison between different types of substance a difficult matter. Even within the same
lQ8
D. N. Hendrickson, J. M. Hollander, and W. L. Jolly, Znorg. Chem., 1969, 8, 2642.
58
molecule. chemical shifts from non-equivalent atoms may be confused with discrete energy loss processes. Caution is therefore advised when considering the data below. The theoretical interpretations of chemical shifts are rather numerous, but can be subdivided into correlations with partial ionic charge, calculation by SCF -MO methods and comparison with empirical quantities. (i) .4tornic c h r g t . . This may be calculated in a number of ways: ( ( I ) from electronegativity. The simplest approach is to use the Pauling method 2 . 1 6 5.149 of estimating the ionic character of a bond A-B from the expression
(i, = 1 -
er;p[-
J.x.4 .
- Xg)7
where s . .xR are the electronegativities of A and B calculated on the Pauling , scale. However, this expression has been extensively criticised. Pritchard and Skinner suggest the expression
6
=
.._
,+5(.~-A
st]) ?.j(.x4 - u , ) ~ +
and Gordy has suggested
4
d,
= (.Y.& - .YJQ = 1
when
(.yA-
.x,l
<2
when
I, - xBI > 2 s
Using this latter expression, T h o r n a ~ obtained a good correlation with C Is ~ shifts in the halogenomethanes. Paulings original method does not usually give a good correlation with X-p.e. data but can be improved by making allowance for the variation of electronegativity with charge following the suggestion of Pauling.oz Fink er a/. 7 9 have used this technique, iterating to self-consistency, in an effort to explain the shifts in gaseous nitrogen compounds, but the results were still not very successful. A more profound analysis by Sanderson203 using a quite different approach gives more realistic partial atomic charges. He assumes that electronegativities may be assigned to molecules as well as atoms, and that all atoms in the molecule take on a common geometric mean electronegativity, but the method has been little investigated in connection with X-p.e. energy data. The Pauling method is extremely easy to use and very rapid. It does, however, suffer the following disadvantages. First, it is clearly dependent on the hybridisation state involved. so double bonds are very difficult to deal with. Second, it will only work when a classical octet structure can be written. In valence bond terms, this means that resonance with structures involving significant charge separation will cause the model to fail. Third, the original Pauling expression was derived from dipole moment measurements on the hydrogen halides and the relationship between this and ionic character is very tenuous.
*O0
201
??
lo
L. Pauling, The Nature of the Chemical Bond, New York, 1960, third edn. H . 0. Pritchard and H . A. Skinner, Chem. Reo., 1955, 55, 773. W. Gordy, Discuss. Faraday SOC.,1955, 19, 14. L . Pauling, The Nature of the Chemical Bond, New York, 1940, second edn. R . T. Sanderson, J . Chem. Educ., 1951, 29, 532; 1954, 32, 2, 238.
59
(b)from semi-empirical calculations. Both extended Huckel and calculations of the CNDO type have been used together with some form of orbital partitioning (usually by the Mulliken method). Used in this fashion, both give results which are rarely any improvement over the much simpler electronegativity methods. suggested that incorporating an intramolecular However, Siegbahn et Madelung potential might substantially improve this correlation. Such was indeed found to be the case in their gas-phase C Is results,j but Pelavin et found no improvement when they tried to correlate P 2 p shifts in a range of solid phosphorus compounds. Hendrickson et al. 19' attempted correlations of both CNDO and extended Huckel calculations with N 1s shifts in the solid state, but found that two lines could be drawn, one roughly correlating the shifts of neutral molecules and the other of anions. They suggest that this may be an artifact of the CNDO method, which overestimates electron repulsion, or else arises from the different lattice potentials associated with ionic or neutral lattices. The same group was more successful in explaining gas-phase shifts.' 7 9 The same method has also been applied to solid-state C Is levels by Gelius et al.'87,188 and by Hendrickson et ~ 1 1 . lThe latter group found a simple correlation with ~ ~ CND0/2 partial atomic charges, which appears to be somewhat fortuitous in the light of the more extended work of Gelius et ul."* where the molecular potential term was found to be essential. However, calculations of partial charges have been criticised by Nordberg et ~ 1 . in ~their investigation of Si 2 p shifts. They l ~ argue that the charge distribution calculated by any SCF-MO theory is a 'book-keeping entry', exceedingly sensitive to the choice of basis set. (ii) Intramolecular potential. Gelius et aL204 have investigated X-p.e. energy shifts theoretically in a number of simple sulphur compounds. They performed ub initio calculations using the IBMOL TV programme of Clementi, Davis, and Veillard and found that the charge on the sulphur atom, calculated by the Mulliken method was exceedingly sensitive to the inclusion of polarisation functions. They also found it necessary to include an intramolecular potential r/: given by q,,,/Rmn where q, is the charge on the adjacent atom, R,, its distance
~ 1 . ~ 9 ~
m#n
from nucleus n, the centre of core orbital given approximately by

AEi
=
$i.
The chemical shift AEi is then
kq,
+ +1
where k is a proportionality constant and 1 a constant depending only on the choice of reference level. This expression holds quite well with roughly proportional to qn thus explaining the fair success of simple charge correlations with shift. A more profound discussion of the potential term has been given by B a s ~ h , ~ ' ~ who argued that if a potential r/; were defined as
K=2
C (4j(1)I1/rlnI$j(1))
j+i
C
mtn
Zm/Rmn
where 2, is the nuclear charge at centre rn, then the variation of V, should parallel
'04
205
U. Gelius, B. Roos, and P. Siegbahn, Chem. Phys. Letters 1970, 4, 471. H. Basch, Chem. Phys. Letters 1970, 5 , 3 3 7 .
60
the (negative of the) orbital energy. - E ~ , which by Koopmans' theorem46 should reflect the ionisation potential from 4i. Calculations on the fluoromethanes using a 'double-zeta' basis set have borne this out. Basch also demonstrated a close connection between and the diamagnetic shielding term obtained from n.m.r. measurements. Schwartz206found a correlation between and A(-ci) for a wider range of compounds of first-row elements than Basch had considered. Again using 'double-zeta' calculations. carbon. nitrogen, oxygen. and fluorine shifts could be fitted to a straight line. In a later paper'" Schwartz uses the non-iterative extended Huckel method of HofTmann2" to calculate V, but the correlation with experimental data is not very impressive. In the fluoromethanes the method considerably overestimates the polarity of the bonds, predicting shifts far in excess of those found. (iii) Energ!. ctrlcirlariotis usitig SCF- M O rheorits Two methods might in principle be used : calculations of both molecule and ion separately, the so-called 'direct' method, or calculation on the neutral molecule alone using Koopmans' theorem to estimate ionisation energy. The direct method clearly corresponds to a process in which relaxation is allowed to occur before the electron is remote from the molecule. The latter method corresponds to a vertical transition. Which process corresponds to physical reality is still uncertain. BagusZo9showed that, for the series F - , Ne. Na' and for C1-, Ar, K + , Koopmans' theorem gave very poor quantitative agreement compared to direct calculations even when very accurate Hartree-Fock wavefunctions were employed. Substantially the same conclusion was reached by Gianturco and Coulson'" for the sulphur atom. Both authors neglect relativistic and correlation corrections, though Bagus209 estimated that at most these would contribute about 1 eV each. The direct method was modified by Hedin and Johansson"' who showed that the correction to the Koopmans' eigenvalues to allow for relaxation could be written in the approximate form.
where r/, is a polarisation potential which describes the change in H F potential when electron i is removed. The method is intuitively appealing and seems to give quite good results when intershell relaxation is more important than the corresponding intrashell terms; that is. it is more suitable for the calculation of core binding energies than for valence shell IPS. The most numerically successful calculations using the direct method have been those of Schwartz"' who obtained a value for methane identical to the experimental value reported by Siegbahn ct ~ 1 1 . ~
""
.Io-
"*
''''' *
2'1
", '
M . E. Schwartz. Chrni. Ph3.s. Lcttrrs 1970, 6 , 63 I . M. E. Schwartr. ChPin. Phi..s. Lrrrerv. 1970, 7 . 78. R . Hofmann. J . Chrrn. Ph,,s., 1963. 39. 1397. P. S. Bagus, Phys. Rei.., 1965, 139, A619. F. A . G i a n t u r c o a n d C . A . Coulson. M o l . Ph>,s..1968, 14, 2 2 3 . L. Hedin a n d A . Johansson, Proc. PhJs. SOC. B ) . 1969, 2, 1336. ( M. E. Schwartz. Chem. Phys. Letters, 1970, 5 . 50.
61
Hillier et al. 1 7 2 have discussed the role of relaxation in determining core energy levels but reach no conclusions as to its importance. Basch and Snyder2I3 concluded from Bagus results that relaxation energy might be an insensitive function of molecular environment and so they preferred to use Koopmans theorem. Even though the results are not quantitatively impressive, there is a general correlation with Mulliken atomic charge and, as later work 7 8 has shown, with experimental values. However, this neglect of reorganisation energy is a serious drawback since there is no reason to suppose that it is any more than very approximately independent of structure. (iv) Empirical correlations. (a) Thermodynamic data. If it be assumed that exchange of atomic cores between two different molecules will involve no energy exchange, then it is possible to calculate core shifts (relative to some standard) from thermodynamic data alone. This method has been developed by Finn et to account for shifts in gaseous nitrogen compounds and applied with impressive success. (b) Group-bond parameters. For a closely related group of molecules of the general formula MX,Y,-, where M is some central species whose core level is being measured as a function of X and Y, it is usually found that the M-X and and M-Y bonds can be represented by empirical parameters S,, 6, such that the shift S(M) is given by
S(M) = n6,
+ (z - n)6,
This approach has been used to estimate the C Is level in CH2F23 and has been discussed by Finn et al. 7 9 Some Conclusions. In spite of the meaning of the acronym ESCA few applications of the technique to chemical analysis have been published in 1970. Perhaps the most interesting example is the publication by Davis et al. of results on polywater. This revealed the presence of quantities of Na, K, C1-, NO,-, borates, silicates, and carbonyl compounds but very little water. The carbonyl region of the X-p.e. spectrum shows considerable similarity to that of carboxylic acids, a fact zlso borne out by the i.r. spectrum.14 An interesting example of the general use of ESCA in organic chemistry was given by Farona et al. 1 8 3 who reported some investigation on complexes of SnCI,. To decide whether the ligand NH,COCH=CH, binds to SnCI, through the oxygen or nitrogen, X-p.e. measurements of the N 1s and 0 1s shifts were made. These showed that nitrogen was the ligand atom. The use of X-p.e. spectroscopy in phase studies has been explored by Wolberg et who examined CuO-Al,O, mixtures. They found that with a high surface area of alumina of a high calcination temperature CuAl,O, was found, but under the opposite conditions only a simple binary mixture. illustrates The investigation of solid-state N 1s shifts by Hendrickson et a number of points. The N 1s shifts of ammonia in ammine complexes of Co,
23
H. Basch and L. C. Snyder, Chem. Phys. Letters, 1969, 3, 333. D. L. Rousseau, Science, 1971, 171, 170.
62
Rh"', Ir"', and Cr"' indicate a considerable amount of ammonium character but no such shifts are observed for NO,-. suggesting that back n-bonding may be occurring between the nitrite and the metal. Such bonding may also be present in the cyanide and nitrosyl complexes. An intriguing result is the pronounced nitrosyl N Is shift in Fe(CN),N02-, contrasting with a shift in the opposite direction in C I - ( C N ) ~ N O ~ - . cyanide N 1s binding energy is about The the same in both complexes. so the iron complex could reasonably be formulated Fe"(CN- ) 5 ( N 0 ) and the chromium complex Crl*'(CN-)s(NO-). The structure * of the anion in Angeh's salt, Na2N20,, was also elucidated. Investigations of second-row atoms are at a much earlier stage, except in the case of sulphur. Pelavin et ~ l . , ' ~in their study of phosphorus derivatives, and * when measuring silicon shifts, found the results impossible Nordberg er to correlate with any simple model. However, Nordberg et a/., by rising the Pauling electronegativity method and drawing a line only through those points where no double-bonding is expected. use the deviation of the points corresponding to other molecules as a measure of h - p x bonding in these. Attempts by Pelavin ur nl. to investigate the phosphorus levels in biologically important phosphates unfortunately proved unsuccessful owing to the fact that the shifts are so small as to be well within the error limits of the machine used. In an investigation of the phosphine complexes. Blackburn er deduce that back n-bonding is of major importance. The variation of chemical shift with stoicheiometry has been reported by Ramqvist ut al. * in a series of carbides of vanadium, niobium, and tantalum. This follows earlier work on TiCX2" in which it was found that the binding energy of Ti($,) increased with increasing .Y. A similar result was obtained for vanadium but, curiously, the binding energies of the Nb(3d,) and Ta(4f;) lines diminish with increasing 4. This may be because the 4forbitals in tantalum are still in the v a l t x e region, but for niobium the finding is not easily explained. The authors interpret their results using a simple M O model suggested by Denker216 but a more realistic explanation will probably have to await solid-state calculations. It is clear even from these few examples that a very considerable amount of empirically explicable evidence arises in ESCA spectra. Once the teething difficulties of tIie technique are resolved it may even prove as potentially powerful as other techniques dependent upon shift phenomena, such as n.m.r.
L. Ramqvist, K . Hamrin, G. Johansson. U . Gelius, and C. Nordling, J . Phys. Chem. Solids, 1969, 30, 1835. S. P. Denker, J . Less Common Metals, 1968, 14, 1 .

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1

Electronic Structure and Magnetism of Inorganic Compounds

1938, vol. 24.

' J . W. Cooper and

Electronic Structure and Magnetistn of Inorganic Compounds

2 Ultraviolet Molecular Photoelectron Spectroscopy

Electronic Structure and Magnetism of Inorganic Compounds

G. Herzberg, 'Spectra of Diatomic Molecules,' Van Nostrand Reinhold, Princeton,

Electronic Structure and Magnetism of Inorganic Compounds

I . Asinovskii, V . A. Kirillin, and V . V. Markovets, Teplofiz. r j s o k . Temp. 1970,

Electronic Structure and Magnetism o Inorganic Coinpounds f

1, 13, 16, 49, 52, 71 15

1,69, 7 1 4 D2) 1, 16, 52, 72 1, 72 1, 30, 72, 73

NO2 H2S XeF, XCN HCN HgX2

1, 75, 77, 78 1, 79 80 81, 82 (Cl, Br, I) 1 83 (C1, Br, I)

1 (+ HDCO, D,CO) 1, 30 ( + ND3), 84 ( f ND,) 1, 85

NF, px3 AsX, HNCO HNCS

85 86 (F, C1. Br, I), 87 (F)

86,88 86 (F, C1, Br), 89 (F), 1 1 1 (F) 86 90 90

Electronic Structure and Magnetism of Inorganic Compounds

92 (Cl. Br, I ) 92 (Cl-Br, Cl--I, Br-I)

HCOOH CH4 SiH,

GeX, SnX, TiX4 VCI, C,O, H2C=C0

96 (Cl, Br) 96 (Cl, Br) 96 (Cl, Br), 99 (CI)

1 1 . 86 (F, CI, Br, I), 93, 59(F)

I , 30.49 ( + CID,) 1.81 (+EtCN). 100 ( + CD,CN)

F2C=CCl CH2CICN CHC1,CN CCI,CN

H,C=CX2 X,C =cx HClC=CHCl F,C=CHCI F,C =CFCl

HCONH, HC-C-C_CH (CHO), N2H4

101 81 81 81 83 (C1, Br, 1) 1 ( + HCONHMe. HCONMe,) 1 ( + DCFC-C=CD)

1 103 ( Me, Ph, and PhCH, derivatives)

1, 86, 104 86 86 86 1,100

Cr(hfa), Co(h fa), Al(hfa), Cr(CO),

w(c0)6 (n-c 5 (n-c g H (n-C5 H

113a 113, 113a 113a 1 1 I 1 ( Mg compound), 70 1 1 1

enolate anion of hexafluoroacetylacetone.

Electronic Structure and Magnetism o Inorganic Compounds f

83 (CI, Br, I ) 83 (Cl, Br, I)

116 116, 117

1 120 124. 1 2 4 ~ 124, 124a

P. Bischof, J. A. Hashmall, E. Heilbronner, and V. Hornung, Tetrahedron Letters,

P. Bischof, J . A. Hashmall, E. Heilbronner, and V. Hornung, Tetrahedron Letters,

Electronic Structure and Magnetism of Inorganic Compounds

P. E. Cade, K . S. Sales, and A . C. Wahl, J . Chem. Phys., 1966,44, 1973.

* However, tolerance limits can usually be placed o n this error.

Electronic Structure and Magnetism of Inorganic Compounds

Electronic Structure and Magnetism of Inorganic Compounds

(Reproduced by permission from 'Molecular Photoelectron Spectroscopy,' Wiley,

Electronic Structure and Magnetism of Inorganic Compounds

Electronic Structure and Magnetism of Inorganic Compounds

1 ' 1 ' 1 6000 8000 10000

Figure 11 The first band in the He' p.e. spectrum of MeCl

Electronic Structure and Magnetism o Inorganic Compounds f

Electronic Structure and Magnetism of Inorganic Compounds

CH4 SiH, GeH,

SF, SeF, TeF, UF,

Electronic Structure and Magnetism of Inorganic Compounds

Electronic Structure and Magnetism of Inorganic Compounds

18 1 6 14 12 IONI AT I0N E NE RGY Z

Electronic Structure and Magnetism of Inorganic Compounds

3 X-Ray Photoelectron Spectroscopy

Electronic Structure and Magnetism of Inorganic Compounds