Electronic supplementary information to accompany
UV photolysis of 4-iodo-, 4-bromo- and 4-chlorophenol:
competition between C–Y (Y = Halogen) and O–H bond fission.
Alan G. Sage, Thomas A.A. Oliver, Graeme A. King, Daniel Murdock, Jeremy N. Harvey
and Michael N.R. Ashfold
School of Chemistry, University of Bristol, Bristol, U.K., BS8 1TS
Table S1
Calculated anharmonic wavenumbers (in cm-1) for the normal mode vibrations for the ground
state 4-HOPh radical (Cs symmetry) calculated at the DFT/B3LYP/6-311+G** level, labelled
in Herzberg notation.1
Mode Label
Symmetry
Mode Label
Symmetry
a'
Wavenumber
/cm-1
3838
ν16
a'
Wavenumber
/cm-1
1044
ν1
ν2
a'
3190
ν17
a'
991
ν3
a'
3176
ν18
a'
808
ν4
a'
3171
ν19
a'
615
ν5
a'
3146
ν20
a'
538
ν6
a'
1635
ν21
a'
405
ν7
a'
1593
ν22
a"
948
ν8
a'
1480
ν23
a"
911
ν9
a'
1435
ν24
a"
808
ν10
a'
1327
ν25
a"
782
ν11
a'
1308
ν26
a"
660
ν12
a'
1266
ν27
a"
479
ν13
a'
1185
ν28
a"
407
ν14
a'
1169
ν29
a"
293
ν15
a'
1100
ν30
a"
242
Table S2
Calculated anharmonic wavenumbers (in cm-1) for the normal mode vibrations for the ground
state 4-IPhOH, 4-BrPhOH and 4-ClPhOH radicals calculated using DFT at the DFT/B3LYP
level of theory, labelled according to Wilson notation.2 The 6311+G** basis set was used for
calculating wavenumbers for the 4-BrPhO and 4-ClPhO radicals, but is unsuitable for
calculations involving elements lying below period 3: thus the DGDZVP basis set was used
when calculating the 4-IPhO radical wavenumbers.
Mode
Label
Symmetry
20a
Wavenumber / cm-1
4-IPhO
4-BrPhO
4-ClPhO
a1
3223
3202
3205
13
a1
3207
3186
3189
8a
a1
1577
1573
1579
19a
a1
1500
1495
1495
7a
a1
1416
1418
1419
9b
a1
1171
1171
1170
18a
a1
1047
1054
1079
1
a1
982
985
968
12
a1
808
804
805
6a
a1
589
609
649
2
a1
246
291
379
20b
b2
3222
3200
3205
7b
b2
3208
3186
3190
8b
b2
1501
1497
1495
19b
b2
1434
1428
1419
14
b2
1283
1287
1287
3
b2
1278
1268
1268
15
b2
1112
1111
1110
6b
b2
610
613
616
18b
b2
448
453
455
9b
b2
199
228
274
5
a2
971
980
978
10a
a2
785
787
785
16a
a2
377
379
381
17a
b1
967
967
967
4
b1
851
851
852
10b
b1
709
695
709
16b
b1
493
491
501
17b
b1
259
263
276
11
b1
89
96
107
Table S3
SOC state labels, dominant electronic configurations, vertical excitation energies calculated
at the equilibrium RCI bond length, weights of the respective SOF states from which the SOC
states are derived, and transition dipole moments/polarisations calculated for 4-IPhOH at the
SOC-CASPT2(12/10)/cc-pVTZ level of theory. Z is aligned with the C–I bond axis and the
ring lies in the YZ plane.
State label
Electronic
Energy
(C2v equivalent)
transition
/ eV
Component TDM /
Spin-orbit free state
Debye (axis)
ππ
*
2A''
ππ
*
3.79
98.9% A'
2A' (1B2)
ππ*
3.79
99.4% 3A'
4.03
3
3
0.000
3
3
1A''
3A''
nσ*
3.79
3
0.001(X)
3
0.038(X)
99.3% A'
0.019(Y)+0.000(Z)
83.8% A'' + 15.2% A'
3A' (2A1)
nσ*
4.03
83.6% A'' + 16.2% A'
0.001(Y)+0.064(Z)
4A' (2B2)
nσ*
4.09
95.5% 3A'' + 3,9% 1A'
0.189(Y)
ππ
*
5A''
ππ
*
4.25
71.7% A' + 28.2% A'
5A' (3B2)
ππ*
4.25
99.8% 3A'
4A''
4.25
4.38
3
3
0.464(X)
3
3
0.004(X)
71.6% A' + 28.1% A'
1
0.002(Y)
3
3
6A''
nσ*
7A''
ππ
*
51.9% A'' + 40.0% A' + 7.2% A'
4.42
96.1% A' + 3.6% A'
0.008(X)
6A' (3A1)
ππ*
4.42
99.8% 3A'
0.000
8A''
ππ*
4.43
88.7% 3A' + 5% 3A'+3% 1A''
0.002(X)
3
3
0.047(X)
7A' (4B2)
ππ
*
4.53
99.9% A'
0.279(Y)+0.011(Z)
9A''
nσ*
4.76
83.5% 3A' + 15.4% 1A''
0.000
8A' (4A1)
nσ*
4.78
82.2% 3A' + 16.1% 3A''
0.045(Z)
10A''
nσ*
4.87
1
3
1
53.8% A' + 44.8% A''
1
3
0.354(X)
3
9A' (5B2)
nσ*
5.43
92.6% A' + 3.9 % A'' + 4.5% A'
0.943(Y)+0.002(Z)
10A' (5A1)
ππ*
5.69
96.0% 1A' + 3.9% 3A''
0.047(Y)+3.923(Z)
11A' (6A1)
nσ*
5.96
3
0.004(Y)+0.003(Z)
3
99.5% A'
11A''
nσ*
5.96
99.1 % A'
0.000
12A''
nσ*
5.96
99.1 % 3A'
0.008(X)
Table S4
SOC state labels, dominant electronic configurations, vertical excitation energies calculated
at the equilibrium RCCl bond length, weights of the respective SOF states from which the
SOC states are derived, and transition dipole moments/polarisations calculated for 4-ClPhOH
at the SOC-CASPT2(12/10)/cc-pVTZ level of theory. Z is aligned with the C–Cl bond axis
and the ring lies in the YZ plane.
State Label
Electronic
Energy
Proportions of spin-orbit free
Component TDM /
transition
Debye (axis)
/ eV
states
2A'
ππ
*
3.81
3
100% A'
0.000
1A''
ππ*
3.81
99.6% 3A'
0.000
2A''
ππ
*
3A''
ππ
*
4.18
4A''
ππ*
3A'
ππ*
4A'
ππ
*
4.43
100% A'
0.000
5A''
ππ*
4.43
100% 3A'
0.000
6A''
ππ*
4.43
100% 3A'
0.000
5A'
ππ
*
ππ
*
6A'
3
0.000
3
100% A'
0.000
4.18
100% 3A'
0.000
4.18
100% 3A'
0.000
3.81
4.51
5.92
99.6% A'
3
1
0.565(Y)+0.005(Z)
1
0.293(Y)+1.924(Z)
100% A'
100% A'
Figure S1
Spin-orbit resolved PECs for 4-IPhOH as a function of RC–I, calculated at the SOCCASPT2(12/10)/cc-pVTZ level with all other degrees of freedom clamped at the MP2 ground
state equilibrium values. The adiabatic outputs have been approximately diabatized by
inspecting the energies and wavefunction coefficients.
Figure S2
Spin-orbit resolved PECs for 4-ClPhOH as a function of RC–Cl, calculated at the SOCCASPT2(12/10)/cc-pVTZ level with all other degrees of freedom clamped at the MP2 ground
state equilibrium values. The adiabatic outputs have been approximately diabatized by
inspecting the energies and wavefunction coefficients.
1
G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules, Van Nostrand, (1945).
2
E.B. Wilson, Phys. Rev. 45, 706 (1934).