Supplementary Material to JMS-15-31
The vacuum-ultraviolet photoelectron spectra of CH2F2 and CH2Cl2 revisited
Richard Tuckett,1,* Jonelle Harvey,1,$ Patrick Hemberger,2 and Andras Bodi 2
1. School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
2. Molecular Dynamics Group, Paul Scherrer Institut, CH-5232 Villigen, Switzerland
*
$
Author for correspondence: (E) r.p.tuckett@bham.ac.uk, (F) +44 121 414 4403, (T) +44 121 414 4425.
Current address: Royal Society of Chemistry, Thomas Graham House, Milton Road, Cambridge CB4 0WF, UK
1
Table S1. Energies, separations from origin band, relative intensities and assignments of vibrational bands
~
in the first photoelectron band of CH2F2, ionisation to X + 2B1, as predicted by harmonic calculations. Only
bands with intensity greater than 10 % of the strongest band, the 220 310 combination, are shown.
Energy / eV
12.727 a
12.862
12.887
12.998
13.022
13.043
13.047
13.133
13.158
13.166
13.178
13.182
13.203
13.207
13.293
13.314
13.318
13.338
13.342
13.363
13.449
13.453
13.474
13.478
13.498
13.609
13.634
a
Relative intensity
3.1
7.4
4.1
7.6
9.8
2.2
2.9
4.1
10.0
1.0
6.0
7.0
3.0
1.5
5.5
6.8
7.2
8.1
3.6
2.2
4.3
3.9
9.3
3.7
5.9
5.8
6.8
Assignment
000
10
310
220
10310
110
320
230
220 310
210310720
110210
210320
110310
330
230 310
110220
220320
110210 310
210330
110320
110230
230 320
110220310
220 330
110 210 320
110 230 310
110 220 320
Set to our experimentally-determined value.
2
Table S2. Energies, separations from origin band, relative intensities and assignments of vibrational bands
~
~
in the first and second (overlapping) photoelectron bands of CH2Cl2, ionisation to X + 2B2 and A + 2B1, as
predicted by harmonic FranckCondon calculations. Apart from the weak bands at low energy below 11.34
eV (11.40 eV) where there is no overlapping problem, only bands with intensity greater than 10 % of the
~
~
strongest band, the 4170 (310) component of X + 2B2 ( A + 2B1), are shown.
~
CH2Cl2+ A + 2B1
~
CH2Cl2+ X + 2B2
Energy / eV
11.228 a
11.230
11.266
11.268
11.302
11.304
11.306
11.340
11.342
11.377
11.379
11.415
11.417
11.453
11.455
11.475
11.477
11.491
11.492
11.513
11.515
11.528
11.530
11.551
11.553
11.566
11.588
11.604
11.626
11.641
11.664
11.679
11.702
11.717
11.724
11.739
11.755
11.762
11.777
11.792
11.799
11.815
Relative intensity Assignment
0.5
0.5
0.9
0.5
0.7
1.3
0.5
1.2
1.8
2.1
2.1
3.3
2.2
4.7
2.0
1.3
1.2
6.3
1.5
2.1
1.3
7.8
1.0
3.0
1.2
9.0
4.1
9.7
5.1
10.0
6.0
9.7
6.6
9.0
1.9
6.9
7.9
2.3
6.8
6.6
2.5
6.4
471
482
481
492
480
491
4102
490
4101
4100
4111
4110
4121
4120
4131
4100 310
4111 310
4130
4141
4110 310
4121 310
4140
4151
4120 310
4131 310
4150
4130 310
4160
4140 310
4170
4150 310
4180
4160 310
4190
4140 320
4170 310
4200
4140 320
4180 310
4210
4160 320
4190 310
Energy / eV
Rel. Intensity
Assignment
11.281
0.4
401
11.317 b
8.7
000
11.320
1.6
411
11.356
1.3
410
11.360
0.5
421
11.399
0.6
720
11.404
10.0
310
11.407
1.8
310 411
11.433
1.5
310 410
11.491
5.1
320
11.578
1.5
330
__________________________________
a Set so that the adiabatic ionization energy
of this state is 11.0 eV.
b Set to our experimentally-determined value.
3
Table S3. Energies, separations from origin band, relative intensities and assignments of vibrational bands
~
~
in the second and fourth (overlapping) photoelectron bands of CH2F2, ionisation to A + 2B2 and C + 2A2, as
predicted by harmonic FranckCondon calculations. Only bands with intensity greater than 10 % of the
~
~
strongest bands, the 4110 310 (310 or 310 410) components of A + 2B2 ( C + 2A2), are shown.
~
CH2F2+ C + 2A2
~
CH2F2+ A + 2B2
Energy / eV
14.702 a
14.769
14.773
14.836
14.840
14.903
14.907
14.912
14.970
14.974
14.979
15.037
15.041
15.046
15.104
15.108
15.113
15.117
15.159
15.164
15.171
15.176
15.180
15.184
15.238
15.243
15.247
15.251
15.298
15.305
15.310
15.314
15.318
15.365
15.372
15.377
15.381
15.385
15.432
15.436
15.439
15.444
15.448
15.452
Relative intensity Assignment
1.4
2.4
1.2
3.5
2.4
4.5
4.0
1.0
5.3
6.0
2.0
5.7
7.8
3.3
5.5
9.3
5.0
1.1
1.1
1.2
5.0
10.0
6.6
1.8
4.2
9.8
7.9
2.7
1.8
3.3
8.9
8.6
3.7
1.9
2.4
7.5
8.5
4.4
1.9
1.5
1.6
5.9
7.8
4.8
460
470
450 310
480
460 310
490
470 310
450 320
4100
480 310
460 320
4110
490 310
470 320
4120
4100 310
480 320
210 330
4100 210
480 210 310
4130
4110 310
490 320
470 330
4140
4120 310
4100 320
480 330
4100 210 310
4150
4130 310
4110 320
490 330
4110 210 310
4160
4140 310
4120 320
4100 330
4120 210 310
4100 210 320
4170
4150 310
4130 320
4110 330
Energy / eV Relative intensity Assignment
15.570 b
5.1
000
15.631
5.0
410
15.690
2.2
420
15.698
10.0
310
15.758
10.0
310 410
15.817
4.3
310 420
15.826
9.1
320
15.885
9.3
320 410
15.945
4.1
320 420
15.953
5.2
330
16.013
5.4
330 410
16.072
2.4
330 420
16.080
2.0
340
16.140
2.1
340 410
16.199
1.0
340 420
__________________________________
a
Set so that the adiabatic ionization energy
of this state is 14.3 eV.
b
Set so that the adiabatic ionization energy
of this state is 15.57 eV.
4
Table S4. Energies, relative intensities and assignments of vibrational bands in the first and second
~
(overlapping) photoelectron bands of CH2F2, ionisation to D + 2B2, as predicted by harmonic
FranckCondon calculations. Only bands with intensity greater than 10 % of the strongest band, the 360
~
component of D + 2B2, are shown.
Energy / eV
18.211 a
18.265
18.317
18.370
18.422
18.476
18.528
18.530
18.581
18.602
18.633
18.635
18.687
18.708
18.739
18.741
18.762
18.792
18.813
18.844
18.846
18.898
18.949
19.055
a
Relative intensity
1.9
1.3
4.5
3.1
7.6
5.3
9.8
1.3
7.0
1.3
10.0
1.7
7.2
1.7
8.3
1.8
1.2
6.1
1.7
5.6
1.6
4.2
3.1
1.5
Assignment
320
320 410
330
330 410
340
340 410
350
340 420
350 410
340 210
360
350 420
360 410
350 210
370
360 420
350 210 410
370 410
360 210
380
370 420
380 410
390
3100
Set so that the adiabatic ionization energy of this state is 18.0 eV.
5
Table S5. Energies, separations from origin band, relative intensities and assignments of vibrational
~
~
bands in the third and fourth (overlapping) photoelectron bands of CH2Cl2, ionisation to B + 2A1 and C + 2A2,
as predicted by harmonic FranckCondon calculations. Only bands with intensity greater than 10 % of the
~
~
strongest band, the 420 (410) component of B + 2A1 ( C + 2A2), are shown.
~
CH2Cl2+ C + 2A2
~
CH2Cl2+ B + 2A1
Energy / eV
12.114 a
12.150
12.150
12.186
12.221
12.257
12.257
12.262
12.292
12.293
12.298
12.328
12.328
12.360
12.364
12.364
12.395
12.431
12.466
a
b
Relative intensity Assignment
1.8
1.6
3.0
7.7
10.0
1.2
8.6
1.0
1.7
5.5
1.1
1.4
2.8
1.4
1.0
1.2
1.8
1.5
1.0
401
411
000
410
420
441
430
410 310
451
440
420 310
461
450
410 210
471
460
420 210
430 210
440 210
Energy / eV
12.214 b
12.250
12.282
12.284
12.302
12.315
12.317
12.338
12.351
12.372
12.406
12.426
12.460
Rel. Intensity
2.5
9.7
1.3
10.0
1.0
1.7
4.8
4.3
1.5
4.5
2.3
1.0
1.0
Assignment
401
000
421
410
401 310
431
420
310
430
410 310
420 310
320
410 320
Set so that the adiabatic ionization energy of this state is 12.15 eV.
Set so that the adiabatic ionization energy of this state is 12.25 eV.
6