Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Ionization potentials have been calculated for all the elements up to Z = 103 for all states of
ionization. The calculations are based on a simple spherical shell solution for neutral atoms. The
average deviation of the calculated ionization potentials from experimental values was found to be
about 5%. A simple method is also given for estimating the binding energies of electrons in all
shells of a multiply charged ion from the calculated ionization potentials.
* Oak Ridge Associated Universities student trainee, summer 1968, from CorneU University
-~Operated by Union Carbide Corporation under contract with the U.S. Atomic Energy Commission
63
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
CONTENTS
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Approximate Solution for Ionization Potential
Binding Energies of Multiply Charged Ions
TABLE I. Comparison of Calculated Ionization Potentials with Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
TABLE II. Average Error of Approximate Solution of Ionization Potential as a Function of Ionization S t a t e . . . 69
TABLE III. Comparison of Calculated Binding Energies for Mo 7+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
TABLE IV. Ionization Potentials for Elements from Z = 2 to Z = 103 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
INTRODUCTION values and mean radii of the neutral atoms only. Values
computed by such an approximation are given in this
In recent years there has been an increasing need paper for ionization potentials of all elements up to
for knowledge of the binding energies of electrons in lawrencium (Z = 103) for all states of ionization.
multiply charged ions and particularly of the binding
energy of the least-bound electron, that is, the ioniza-
tion potential. Information on the nature and extent of Approximate Solution for Ionization Potential
the ionization in stellar atmospheres is obviously im-
If one regards the atom as a set of concentric
portant for the interpretation of stellar spectra. Data
spheres, the binding energy of an electronic shell nj
on ionization potentials for highly charged ions also
in the ground state of an ion with charge N, e.,j (N),
would be most welcome in studies of the preparation
can be obtained from the binding energies e.,~ (0) and
of ion sources for heavy-element production and in
mean radii ?n~j of the neutral atom by the following
studies of fission in which beams of highly charged
relationship:
recoil ions are analyzed.
A large number of experimental values for the ~(n,j),(N) = e(.,C(O) + ~ qn,~(N) [if ?-nij -> ~n~j)*]
ionization potentials have been determined for multiply n*j rn~j
charged ions of the lighter elements. Through interpola- (1)
tion and extrapolation Lotz a was able to obtain fairly + ~ qn,j(N) [if Fn~J. < g(n,j)*]
good values for all the ions of elements from Z = 1 to
30. Above this range it is no longer possible to make
good estimates from experimental results since the data where q,aj(N) is the number of electrons removed from
are very sparse. However, binding energies may be ob- shell nlj for an ion having charge (N). An asterisk is
tained from atomic wavefunctions as derived from the used to indicate the orbital whose energy is being cal-
self-consistent-field (SCF) methods of Hartree and Fock. culated. In the calculation of a set of ionization poten-
The availability of high-speed computers has made it tials of a given element, en~j(0) and ?-n~jare taken from
possible to carry out such calculations in a comprehen- the eigenenergies and mean radii as obtained from SCF
sive manner, both in the nonrelativistic and relativistic solutions for the neutral atom. The first ionization po-
approximations. tential is the eigenenergy of the least-bound orbital in
For purposes of comparison we present in this the atom. Values of e(n~j)*(1) are then calculated for
paper results from SCF solutions of a number of ioniza- each of the orbitals using Eq. (1). The second ioniza-
tion energies for a variety of elements. Fairly compre- tion potential is the energy required to remove the
hensive calculations have been made elsewhere for ions, electron from the least-bound orbital of the singly
particularly for the light elements2 ,a However, such charged ion. An electron is now assumed to be removed
lengthy calculations are almost prohibitive for all of the from this orbital, and the calculation proceeds until all
ionized states of all the elements from helium to law- the ionization potentials have been determined. As will
rencium since 5355 values are involved. Fortunately, be shown, surprisingly good agreement was obtained
one can devise a simple approximation for obtaining between experiment and the results of this simple
ionization and binding energies that requires the eigen- method of estimating the ionization potentials.
64
IONIZATION POTENTIALS
As an example of how the calculation by means to a cancellation of errors. That the general approach,
of Eq. (1) works, let us take boron. The mean radii and however, is valid is demonstrated by the employment in
eigenvalues for the atom are the following: Eq. (1) of a still better approximation for 1/i, viz.,
Shell e(eV) ?" (Bohr Radii)
ls 209.45 3.257 /_=
28 13.47 1.976
2/) 8.43 2.205
where +(r) is the single-electron wavefunction for the
atom as determined from an SCF solution. This treat-
The first ionization potential or the minimum energy ment did seem to improve the results slightly but not
to remove an electron from neutral boron is sufficiently to warrant the greatly increased computa-
tion time required to evaluate the integrals. The use of
e2a,(0 ) = 8.43 eV.
1/7 offers the simplest solution which still gives a good
Removal of the 2p Y2 electron results in the following fit to experiment.
binding energies for the singly charged ion. For our calculations we used the eigenvalues and
mean radii for free atoms as obtained from relativistic
Is) %o,(1) Hartree-Fock wavefunctions computed at Los Alamos. 4
For unfilled shells the solutions are based on j - j cou-
=q,0,(0)+_q 27.21
r%1,1/~ pling and a finite nuclear size. In TABLE I we have
compared our approximate calculations of the ioniza-
= 209.45 + ~ 1 27.21 = 221.79 eV. tion potentials with experiment. Unfortunately, the
experimental data are rather sparse for elements with
2s) %,o,(1)
Z greater than 30, but we have tried to make the
= ez,o, (0) + _ q 27.21 comparison as comprehensive as possible. Nowhere does
r2,1, the calculation collapse. It gives reasonable results for
1 heavy as well as light elements, for the highly charged
= 13.47 + ~ 27.21 = 25.81 eV. ions as well as for the first few ionization potentials. The
average percent deviation between experiment and cal-
The second ionization potential or minimum energy to
culation, < [Ae[ >, for values given in TABLE I is 4.9%
remove an electron from B +a is 25.81 eV.
where
Removal of the 2py~ and 2s electrons results in
the following binding energies for the doubly charged E(X) - E(A)
ion: Ae(A) = X 100. (3)
E(X)
1S) el, O, (2)
The ionization potentials, E ( X ) and E(A) are obtained,
=q,o,1/~ ( 0 ) + [ q + _ q ] X 27.21 respectively, from experiment and from our approxi-
r-2,1, rz,o, mate calculation using Eq. (1). We found a value of
5.3% for <lAeJ > when we compared our values with all
= 2 0 9 " 4 5 + [ 2 ~. 2 + 1 . 9 ~ ] 27"21 of the ionization potentials reported by Lotz I as ob-
= 235.56. tained from semiempirical extrapolations.
We also compared our results with essentially all
2s) e2,o, (2) q
r q q of the available experimental data obtained from opti-
[ + j 27.21 cal data as compiled by Moore. 5 The average error,
72,1, r2,o4 which is defined by Eq. (3), is given as a function of the
degree of ionization in TABLE II. In general, the error
= 13.47 + [ 2 . 2 ~ + 1.@76] 27.21 is 5% although it is slightly higher for the first few
ionization potentials; however, for these cases the abso-
= 39.58 eV.
lute error in terms of eV is smaller. Finally, we can
The third ionization potential or minimum energy to assess the approximate method in the case in which the
remove an electron from B+2 is 39.58 eV etc. last electron is removed from an atom since it is a
A better approximation than 1/? would seem to hydrogenic ion. Using the first-order relativistic for-
be <1/r>. However, use of this value rather than 1/~ in mula 6 and including a slight correction for finite size
Eq. (1) leads to substantially poorer agreement with for the heavier ions, we have determined the last ioniza-
experiment. The success of ~ is apparently in part due tion potential for all of the elements up to lawrencium.
65
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
On comparison with the approximate solution an aver- case) and the radius of the last electron removed to
age deviation of 2.7% is found. form A ~+ is also equal to or greater than the radii of
Also included for comparison in TABLE I are the other ionized electrons, the binding energies of the
results based solely on SCF calculations, individual solu- shells n~j* in AN+ are given by
tions being obtained for each ion. The ionization poten-
tial in accordance with Koopmans' rule was taken as e(n~j)*(N) = [/(fir) _ q~j),(0)] + q~)*(0), (4)
the eigenvalue of the most loosely bound shell. Ioniza-
tion potentials also may be obtained by taking the where I(N) is the ionization potential of ion AN+ as
difference in total energy between the initial and final given in TABLE IV, e(~j),(0) is the binding energy in
states before and after ionization. In principle, this the neutral atom corresponding to the least tightly bound
should lead to a better value, but generally the improve- orbital in AN+, and e(,~j)*(0) is the binding energy in
ment is not large. 7 For the lighter elements we have the neutral atom corresponding to the orbital (nlj)*.
used Clementi's results, 2 which are from nonrelativistic The binding energies, %~j)*(0) and e(,o),(0), can be
Hartree-Fock solutions based on an L-S coupling scheme obtained from Ref. 4 and also from a tabulation of
for the lowest term value for unfilled shells. For heavier Carlson and Pullen9 or from a table of experimental
elements one needs a relativistic solution, and we have binding energies. 1 Values of 7 for the neutral atom may
employed our own Dirac-Fock-Slater codes with finite be obtained from the calculations given in Ref. 4 or
nucleus, which uses Slater's approximate potential for from relativistic Hartree-Fock-Slater calculations1~ or
exchange and/toes not employ a coupling scheme for from nonrelativistic solutions?2 The value in brackets
unfilled shells. Comparison of the results in TABLE I can be thought of as the total potential of the removed
demonstrates that the use of SCF solutions gives agree- electrons that was felt by the inner shell electrons. In
ment with experiment that is roughly better by a factor the odd chance that the radius of the least-bound
of two for the lighter elements, although no substantial electron in AN+ is less than the orbital in question, i.e.,
improvement is noted for the heavier elements. In the (nlj)*, one may add to Eq. (4) the correction:
latter case a better approximation for exchange would
help considerably for the first few ionization potentials. q,o + q-~J [ifTn~j < 7~j), and 7~0 < 7(,0)*]
It might be expected that agreement with experiment r(n~ j)' r(rd 9
would improve markedly if one had experimental values
for higher ionization potentials with which to compare. or (5)
High-speed computers make a complete calculation,
using the SCF method, of all the ionization potentials qn~j + qn~j [ifT,# < 7(n#), andTn# > 7 *
a possible, but still very tedious, undertaking; and the
improvement over the approximate calculation is only
where 7~n~j), is the radius of the least tightly bound
modest. To make a substantial improvement would
orbital in AN+, ~,~# is the radius of a shell in which
require the handling of an intermediate coupling scheme
electrons have been removed to form AN+, and 7~n~j)* is
for heavy elements and corrections for second-order
the radius of the shell whose binding energy we are
relativistic effects. For all elements some way to handle
calculating, viz., %aj)*(N). All radii can be estimated
electron correlation will be needed. At the present time
from those corresponding to the appropriate orbital in
calculations employing all these improvements would
the neutral atom.
be too complex for any comprehensive calculation. Since
As an example of binding-energy calculation let
in many applications values of 5% accuracy are quite
us take the case of Mo z+. The last electron removed to
adequate, it seems prudent to present a complete list
of the approximate values of the ionization potentials form Mo z+ is from the 4p3/2 shell and has a radius
with the hope that more definitive calculations will (estimated from the neutral atom) that is smaller than
become available some time in the future. either the 4d or 5s shells yet larger than any of the
other shells that make up Mo 7+. Thus, Eq. (4) is valid
as stands. From TABLE IV, I(N) the ionization potential
for Mo 7+, is 146 eV. The binding energy e(n~j),(O)for the
Binding Energies of Multiply Charged Ions
4pa/2 shell in neutral Mo is 48 eV according to Ref. 9.
It is a relatively simple matter to extract good The remaining orbital energies for Mo also are taken
estimates for the binding energies of electrons in any from Ref. 9. The approximate binding energies as cal-
shell of a multiply charged ion from the ionization culated from Eq. (4) are given in TABLE III. For com-
potentials given in TABLE IV. If a shell of an A N+ ion parison, eigenvalues are given for a direct relativistic
has a mean radius equal to or less than the radii of the Hartree-Fock-Slater solution for Mo 7+. The agreement
electrons removed to form A N+ (which is usually the is quite good.
66
IONIZATION POTENTIALS
67
CARLSON, NESTOR, W A S S E R M A N , A N D M c D O W E L L
TABLE I
Comparison of Calculated Ionization Potentials with Experiment
C Z - 6 AI Z - 13 Ca Z gO Fe Z - 26
ION E(X) E(A) A~(A) E(S) a~(S) E(X) E(A) a~(A) E(S) a~(S) E(X) E(A) a~(A) E(S) a~(S) E(X) E(A) A~(A) E(S) a~(S)
Neutral ii.3 i0.6 +6.2 ii.8 -4.4 6.0 5.7 +5.0 5.7 +5.0 6.1 5.3 +13.i 5.3 +13.1 7.9 7.2 +8.9 7.0 +ii.4
+i 24.4 26.1 -7-0 24.6 -0.8 18.8 i8.7 +0.5 17.8 +5.3 11.9 11.8 0.8 11.3 + 5 .O 16.2 15.7 +6.2 -
2 47.9 50.4 -5.2 46.1 +3.8 28.4 29.2 -2.8 28 .i +l .i 51.2 49.3 3.7 51.0 + 0.4 30.7 32.7 -6.5 35-8 -16.6
3 64.5 67.6 -4.8 64.4 +0.2 120 116 +5.0 122 -1.7 67.3 70.6 4. 9 68.0 - 1.0 54.8 57.4 -4.7 56.4 - 2.9
4 392 374 +4.6 392 o 154 162 -5.2 157 -1.9 84.5 91.9 8.8 86.7 - 2.5 75.0 83.0 -10.6 77.4 - 3.2
5 490 476 +2.9 490 0 190 207 -8.9 197 -3.4 108.8 113.2 4.0 107.8 + 1.0 99 108 -9.1 i01 - 2.0
6 241 252 -4.6 243 -0.8 128.0 135 5.5 126.7 + 1.0 125 133 -6.4 126 - 0.8
7 284 298 -4.9 286 -0.7 147.6 156 5.4 146.5 + 0. 7 151 158 -4.6 152 - 0.7
8 330 343 -3.9 331 -0.3 188.8 203 7.4 185.6 + 1. 7 235 240 -2.1 234 - 0.4
9 399 427 -7.0 393 +1.5 211 226 7.1 21o + 0.5 262 272 -3.8 263 - 0.4
I0 442 471 -6.6 441 +0.2 592 558 5.7 594 - 0.3 290 303 -4.5 294 - 1.4
ii 2086 1984 +4. 9 2082 +0.2 657 642 2.3 663 - 0.9 331 335 -1.2 328 + 0.9
12 2304 2211 +4.0 2299 +0.2 727 725 0.3 738 - 1.5 361 372 -3.0 358 + 0.8
13 818 808 1.2 820 - 0.2 392 404 -3.1 389 + 0.7
14 895 895 o 894 + 0.I 457 472 -3.3 450 + 1.5
15 974 979 - 0.5 971 + 0.3 490 506 -3-3 485 + 1.0
16 1087 1102 - 1.4 1074 + 1.2 1265 1168 +7-7 1264 + 0.i
17 1157 1178 - 1.8 1151 + 0.5 1358 1283 +5.5 1363 - 0.4
18 5129 4926 + 4.0 5106 + 0.4 1456 1399 +3.9 1467 - 0.8
19 5470 5280 + 3.5 5442 + 0.5 1582 1514 +4.4 1581 + 0.i
20 1689 1644 +2.7 1681 + 0. 5
21 1799 1760 +2.2 1785 + 0.8
22 1950 1923 +1.4 1924 + 1.3
23 2045 2025 +i.0 2024 + 1.0
24 8828 8503 +3.7 8759 + 0.8
25 9278 8969 +3.3 9197 + 0. 9
< I A~I) 5.1 1.5 4.9 1.7 4.1 1.6 4.5 2.1
Br Z = 35 Mo Z = 42 Sn Z 50 Sb Z = 51
ION E(X) E(A) ~ ( A ) E(S) ~(S) E(X) E(A) A(A) E(S) ~(S) E(X) E(A) A~(A) E(S) ~qS) E(X) E(A) AqA) ~(S) ~(S)
Neutrel 11.8 12.3 - 4.2 12.4 -5.1 7.1 5.7 +19.7 6.0 +15.i 7.3 6.6 +9.6 6.1 +16.4 8.6 7.9 +8.1 6.9 +19.8
+i 21.6 25.1 -16.2 22.8 -5.6 16.2 14.6 + 9.9 14.2 +14.1 14.6 15 .i -3.4 13.5 + 7.5 16.5 17.4 -5.5 15.4 + 6.7
2 35.9 38.0 - 5.8 35 .i +2.3 27.1 29-2 - 7.7 2).8 + 4.8 30.5 30.7 -0.7 30.1 + 1.3 25.3 26.9 -5 .i 24. 3 + 4.0
3 47.3 51.2 - 8.2 46.4 +I. 9 46.4 43.4 + 6.5 38.8 +16.4 40. 7 41.6 -2.2 40.6 + 0.2 44.1 45 .i -2.3 43.6 + I.i
4 59.7 64.3 - 7-7 58.4 +2.2 61.2 57.6 + 5.9 52.9 +13.6 72.3 73.8 -2.1 76.4 - 5.7 56 57 -1.8 55.1 + 1.6
5 88.6 92.5 - 4.4 84.3 +4.6 68 72 - 5.9 68.1 - 0.i 108 95 +12.0 99.4 + 8.0
6 i03 108 - 4.9 i00 +2. 9 126 124 + 1.7 125 + 0.8
7 196 182 + 5.7 196 -1.6 153 146 + 4.6 144 + 5.9
< [ a~[) 7.1 2.7 7.7 8.9 3.6 6.2 5.8 6.9
Te Z = 52 Pb Z 82 Bi Z - 83
Neutrsl 9.0 9.2 -2.2 8.2 +8. 9 7.4 6.9 +6.8 6 -5 +12.2 7.3 6.8 +6.8 6 .O +17.8
+i 18.6 19.3 -3.8 16.4 +11.8 15.0 15.6 -4.0 14.1 + 6.0 16. 7 17.2 -3.0 15.8 + 5.4
2 31 30 +3.2 26.6 +14.2 31.9 32.3 -1.2 31.6 + 0.9 25.6 96.9 -5.1 24.7 + 3.5
3 38 40 -5-3 36.6 + 3-7 42.3 43.6 -3 .i 42.1 + 0.5 45.3 46.1 -i.8 44.7 + 1.3
4 60 61 -1.7 58-5 + 2. 5 68.8 67.2 +2.3 68. 5 + 0.4 56.0 58.2 I3.9 56.1 0'2
I
E(X) experimental ionizstion potentia!a in eV (cf. ref. i and C. E.Moore~ "Atomic Energy Levels;" Vol. IiI; p. xxxvii (Circulsr of the National Bureau of Standards
467, 1958)).
E(A) C~iculoted ionization potentials in eV using an approximate method (cf. Table IV).
E(S) Calcul~ted ionization potentiels in eV using SCF wave functions. Values from Z - 6 to 35 taken from ref. 2. Values from Z - 42 to 83 based on relativistic
wave function progrem described i~ ref. 8.
= ~ x 100 (%).
68
IONIZATION POTENTIALS
TABLE II
Average Error of Approximate Solution of Ionization
Potential as a Function of Ionization State
TABLE III
Comparison of Calculated Binding
Energies for Mo 7+ (eV)
69
C A R L S O N , NESTOR, W A S S E R M A N , A N D M c D O W E L L
TABLE IV
Ionization Potentials for Elements from Z = 2 to Z = 103
Symbols Explanation
CONFIG Configuration of the ion as given by the least-bound orbital and the number of electrons in that
orbital + = .~ -4- ~/2, - : ~ - ~2
For example, the ionization potential for Sb s+ is 1.746 102 eV and the electron removed is
from 4d5/2 shell which contains 3 electrons
IP Ionization potential in electron volts as calculated from Eq. (1) using input data from Ref. 4
E Exponent
70
IONIZATION POTENTIALS
HE Z = 2. 0 Z = 9. MG Z = 12.
71
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
72
IONIZATION POTENTIALS
73
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
74
IONIZATION POTENTIALS
75
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
76
IONIZATION POTENTIALS
77
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
78
IONIZATION POTENTIALS
79
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
80
IONIZATION POTENTIALS
8]
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
82
IONIZATION POTENTIALS
83
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
84
IONIZATION POTENTIALS
85
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
86
IONIZATION POTENTIALS
87
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
88
IONIZATION P O T E N T I A L S
89
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
90
IONIZATION P O T E N T I A L S
91
CARLSON, NESTOR, WASSERMAN, AND M c D O W E L L
92
IONIZATION POTENTIALS
93
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
94
IONIZATION POTENTIALS
95
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
96
IONIZATION POTENTIALS
9?
CARLSON, NESTOR, WASSERMAN, AND McDOWELL
98
IONIZATION POTENTIALS
99