Electronic Supplementary Information for

A Multi-Pronged Comparative Study of the Ultraviolet

Photochemistry of 2-, 3- and 4-Chlorophenol in the Gas Phase

S.J. Harris, T.N.V. Karsili, D. Murdock, T.A.A. Oliver, A.M. Wenge, D.K. Zaouris,
M.N.R. Ashfold and J.N. Harvey,
School of Chemistry, University of Bristol, BS8 1TS, U.K.

J.D. Few, S. Gowrie and G. Hancock,

Department of Chemistry, Physical and Theoretical Chemistry Laboratory,
Oxford University, South Parks Road, Oxford OX1 3QZ, U.K.

D.J. Hadden, G.M. Roberts and V.G. Stavros,

Department of Chemistry, University of Warwick, Coventry CV4 7AL, U.K.

G. Spighi, L. Poisson and B. Soep,

CNRS, IRAMIS, SPAM, Laboratoire Francis Perrin, URA 2453, F-91191 Gif-sur-Yvette,
France.

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S.1 Further experimental details

FTIR emission studies

An essential difference in the work presented here compared to that reported previously,1
concerns the generation of the excitation wavelengths. 193 nm radiation was provided by an
ArF excimer laser (Lambda Physik COMPex) operating at 10 Hz with a maximum output of
ca. 250 mJ pulse-1 and a pulse length of 25 ns; the energy was reduced to ~50 mJ/pulse at the
entrance to the Welsh cell. 226 nm radiation was produced by pumping a dye laser (SIRAH
PRSC-LG-24) with the 355 nm output of a frequency tripled Nd YAG laser (Quanta Ray
PRO-290-10) and frequency doubling the resulting 452 nm output using a BBO crystal: 5
mJ/pulse, 10 Hz, 10 ns pulse width. 266 nm radiation was obtained as the frequency
quadrupled output of a Nd YAG laser (Spectron SL803-10).

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S.2 Further details of computational methods

DFT calculations of minima and TSs on S0 PES of ClPhOH.

All species were fully optimized at the B3LYP/6-31G(d) level of theory using the Gaussian
03 package,2 and frequency calculations were carried out for all species. Single point
energies were then computed using the 6-311+G(d,p) standard basis set. Where justified by
the molecular structure, lower-energy open-shell singlet solutions were sought using an
unrestricted B3LYP ansatz for both the geometry optimization and the single point
computation. All quoted energies include a correction for zero-point energy using the
B3LYP/6-31G(d) frequencies.

Calculating excited state PECs

ROH

The ground state minimum energy geometry was optimised at the complete active space self-
consistent field (CASSCF) coupled with the aug-cc-pVTZ basis set assigned to the C, N and
O atoms. For Cl, this basis set was extended to include an extra tight d polarisation function
[aug-cc-pV(T+d)Z]. A (10/10) active space comprising ten electrons distributed in the
following ten orbitals was used: three  and three * Hückel type orbitals, the oxygen px lone
pair, the  and* orbitals centred around the OH bond and the 3s Rydberg orbital on the O
atom.

Unrelaxed (rigid body) potential energy curves along ROH were calculated at the complete
active space with second order perturbation theory (CASPT2) in order to describe the
dynamic correlation effects of the various excited states. These CASPT2 calculations were
based on a fully state averaged CASSCF reference wavefunction (SA4-CASSCF), over the
lowest four singlet states with equal weights. An imaginary level shift of 0.5 Eh was used to
aid convergence and circumvent intruder state effects.

The fully relaxed scans for the adiabatic S1 states of 2- and 4-ClPhOH shown in figs. 9(a) and
9(d) of the paper were calculated by stepping ROH from the optimised S1 CAM-B3LYP
structure and, at each ROH, allowing all other internal degrees of freedom to relax to the
minimum energy structure. Single point energies were then recomputed along the so derived
minimum energy pathway at each ROH using the CASPT2(10/10)/cc-pVTZ level of theory.

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Out-of-plane ring deformations

The ground and first excited states and the lowest energy S0/S1 CI of 2-, 3- and 4-ClPhOH
were optimised at the CASSCF(10,8) / 6-31G(d) level of theory. The CASSCF optimisations
of the lowest energy CI required state averaging between the S0 and S1 states, with equal
weights. The equations of the coupled perturbed multi-configurational self-consistent field
(CPMCSCF) were solved during these optimisations and derivative coupling and gradient
differences at each optimisation step determined. The optimised S1 minimum energy and
S1/S0 CI geometries were then connected via a linear interpolation in internal coordinates
(LIIC) using the CASPT2(10,8) / aug-cc-pVDZ level of theory with the aug-cc-pV(D+d)Z
basis set assigned to the Cl atom. The active space for these CASSCF and CASPT2
calculations consisted of 10 electrons in the following 8 orbitals: the three  and three * ring
orbitals and the px orbital on the Cl and O atoms.

RCCl

The geometries of the ground and first excited states of 2-, 3- and 4-ClPhOH were first
optimised at the CAM-B3LYP/6-31G(d) level of theory. Starting from the optimised S1
structure, RCCl was then scanned and, at each chosen value of RCCl, the other internal
degrees of freedom were then allowed to relax to the respective minimum energy structure.
Single point energies were then recomputed along the adiabatic S1 CAM-B3LYP minimum
energy pathway at each RCCl using the CASPT2(12/10)/cc-pVTZ level of theory. The active
space employed in these calculations consisted of the three  and three * ring orbitals, the O
and Cl px orbitals and the  and* orbitals centred around the CCl bond. These
calculations were based on a reference CASSCF wavefunction that was state averaged with
the S0 state.

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S.3 UV absorption spectra of 2-, 3- and 4-ClPhOH

Figure S.3.1 UV absorption spectra of (a) 2-ClPhOH in the gas phase and in solution in
cyclohexane and (b) 3- and 4-ClPhOH in cyclohexane solution.

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S.4 Comparing long wavelength 1+1 REMPI and H atom PHOFEX spectra of 2- and
3-ClPhOH.

2-ClPhOH

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3-ClPhOH

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S.5 Prompt H atom formation following 200 nm excitation of 2-ClPhOH.

Figure S.5.1: (a) H+ velocity map image (inset), and TKER spectrum derived therefrom,
following excitation of 2-ClPhOH at 200 nm and 243.1 nm probing at ∆t = 2 ps. (b)
Integrated H+ signal transient (over the range 12000  TKER  17000 cm–1) and associated
kinetic fit (black line) following excitation at 200 nm. Individual components of the fit,
associated with an exponential rise function of H < 50 fs (red) and an exponential decay
function of H = 180 ± 30 fs (blue), are also shown.

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S.6 Selected TRPE images and analysis

(a) (b) (c)

Figure S.6.1: Raw TRPE images taken for 2-chlorophenol at different pump (266 nm) –
probe (800 nm) time delays, t: (a) before, (b) at, and (c) 1000 fs after autocorrelation, with
the probe laser polarisation aligned vertically and parallel to the detector plane (as shown).
Kinetic electrons imaged at t > 0 display obvious (parallel) recoil anisotropy, whereas the
weak background electron distribution measured at t < 0 is isotropic.

Figure S.6.2: Kinetic energy distribution obtained by summing the P2 component in TRPE
images obtained following 266 nm (pump) – 800 nm (probe) excitation of 2-ClPhOH at time
delays in the range 0 < t < 4 ps, along with a best-fit decomposition in terms of series of
overlapping Gaussian features. The comb above the spectrum shows the predicted energies
of features arising from one photon ionisation of ns Rydberg states, assuming I.P. = 9.0 eV

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and =1.05. The shoulder at Eel ~0.55 eV hints at contributions from a second Rydberg
series.

TRPE images recorded at each t were inverted using the pBasex algorithm 3,4
and their
angular dependence with respect to the probe laser polarization analysed by expansion in a
finite series of even Legendre polynomials. For the present 2-ClPhOH data, the radially
averaged second order (P2) term was summed for time delays, t, between 0 and 4 ps,
yielding the electron energy profile shown in fig. S.6.2 The maximum electron kinetic
energy accords sensibly with that expected on the basis of four (800 nm) photon absorption
from the S1 state (Eel(max) ~ 1.75 eV assuming excitation from the energy of the S1(v=0) level
and an ionisation potential (I.P.) of 8.9 eV 5) and shows clear structure, which we decompose
as a sum of Gaussian functions. This structure is broadly consistent with that expected for
ionisation from a series of ns Rydberg states, which could be populated by ultrafast relaxation
of highly excited valence states (at energies close to the ionisation limit) formed by
absorption of three probe photons, which are then ionised by absorption of a fourth 800 nm
photon. The illustrative assignments shown in fig. S.6.2 (which assume I.P. = 9.0 eV (and
thus Eel(max) = 1.65 eV) and a quantum defect, , of 1.05) reproduce the observed maxima
well, though we note that an alternative assignment assuming a series with ~0 (and n values
one lower than indicated in fig. S.6.2) would fit the structure in the electron kinetic energy
spectrum equally well. The recoil anisotropy of the higher kinetic energy features provides
additional support for the ns series assignment, since one photon ionisation should yield p
electron waves.

The first (lowest energy) maximum in this interpretation would correspond to ionisation from
the 4s Rydberg state, but we recognise that this slow feature likely also involves contributions
from direct three (800 nm) photon ionisation with Eel < 0.1 eV – which we suspect to be the
major contributor to the bright central spot in the measured images. We also note that two
(800 nm) photon excitation from this state would result in electrons with Eel(max) ~ 1.75 eV,
which may contribute at the high kinetic energy end of the spectrum shown in fig. S.6.2.

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S.7 TKER spectra derived from HRAPTS measurements when exciting S1(v>0)
levels of 3- and 2-ClPhOH (left and right hand columns, respectively).

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S.8 FTIR emission studies

HCl vibrational distributions

The HCl fundamental emission was found to contain contributions from vibrationally excited
HCl molecules in vibrational levels with v = 1-3, and the spectra recorded at early times
(when vibrational relaxation is negligible) were analysed to estimate the nascent vibrational
populations. Assuming rotational thermalisation (295 K) was found to produce the best fits.
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Surprisal analyses were used to determine the unobserved v = 0 population in each case.
The surprisal plots were linear, with the slopes indicating a larger than statistical fraction of
the available energy appearing in the form of HCl product vibration. Photolysis at the longer
wavelengths produced less vibrational excitation, as shown in fig. S.8.1,, but the fraction of
the available energy partitioned into the HCl products was found to be approximately
constant, (e.g. ~7% following excitation of 2-ClPhOH at both 193 nm and 266 nm.

Figure S.8.1 Relative vibrational (v) state population distributions of the HCl products
arising from photolysis of a 20 mTorr sample of 2-ClPhOH at 193 nm (o), 226 nm (∆) and
266 nm (□).

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S.9 Calculated harmonic wavenumbers of the normal mode vibrations of 2-ClPhOH
at the (Cs constrained) minimum energy geometry of the S1(1*) state.

mode number harmonic wavenumber / cm-1

1 192
2 153
3 244
4 261
5 354
6 376
7 417
8 486
9 492
10 519
11 553
12 614
13 645
14 671
15 845
16 849
17 1013
18 1060
19 1111
20 1178
21 1211
22 1309
23 1364
24 1463
25 1487
26 1530
27 1565
28 1616
29 3229
30 3253
31 3278
32 3281
33 3689

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Poisson, L. LV_pBASEX, 2009
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