Supplementary Material
Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced
in photochemical reactions of trans-1,3-butadiene and Cl2 in solid para-hydrogen
Mohammed Bahou,1 Jen-Yu Wu,1 Keiichi Tanaka,1 and Yuan-Pern Lee1, 2, a)
1
Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung
University, 1001 Ta-Hsueh Rd., Hsinchu 30010, Taiwan
2
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan
(Received: xx May, 2012; Accepted xx xxxx, 2012)
a)
Author to whom correspondence should be addressed. Electronic mail: yplee@mail.nctu.edu.tw
1
Geometries of trans-1,3-butadien and Cl2-C4H6 predicted with the
B3PW91/6-311++g(2d,2p) method are shown in Fig. S1. Relative integrated line intensities as a
function of the irradiation period with light at 365 nm for the Cl2-C4H6 complex at 914.5 cm1,
trans-1-chloromethylallyl at 809.0 cm1, and 3,4-dichloro-1-butene at 738.8 cm1 are shown in
Fig. S2.
Comparison of vibrational wavenumbers (in cm1) and IR intensities of the
2-chloro-3-buten-1-yl (conformers 2a and 2b) and 1-chloro-1-methylallyl (3) radicals predicted
with the B3PW91/6-311++g(2d,2p) method is shown in Table SI. Comparison of vibrational
wavenumbers (in cm1) and IR intensities of trans-3-buten-1-yl (5a) and cis-3-buten-1-yl (5b)
radicals predicted with the B3PW91/6-311++g(2d,2p) method is shown in Table SII.
2
Table SI. Comparison of vibrational wavenumbers (in cm1) and IR intensities of the
2-chloro-3-buten-1-yl (conformers 2a and 2b) and 1-chloro-1-methylallyl (3) radicals predicted
with the B3PW91/6-311++g(2d,2p) method.
mode
2-chloro-3-buten-1-yl (2a)
2-chloro-3-buten-1-yl (2b)
harmonic
anharmonic
1-chloro-1-methylallyl (3)
harmonic
anharmonic
harmonic
anharmonic
1
2
3273 (3)a
3237 (9)
3124
3103
a
3273(6)
2
3249 (7)
3126
3103
3267 (8)a
3170 (5)
3116
3068
3
4
3166 (4)
3161 (2)
3034
3035
3162 (7)
3159 (12)
3020
3032
3150 (20)
3124 (21)
3020
2982
5
6
7
8
9
10
11
3147 (8)
3131 (2)
1704(2)
1468 (19)
1458 (7)
1345 (1)
1314 (3)
3007
2989
1655
1443
1432
1316
1290
3139 (11)
3089 (6)
1713 (20)
1460 (9)
1439 (24)
1342 (4)
1320 (4)
3004
2973
1681
1433
1402
1306
1294
3077 (20)
3027 (42)
1517 (3)
1493 (4)
1460 (20)
1456 (41)
1408 (9)
2928
2900
1463
1464
1424
1424
1380
12
13
14
15
16
17
18
19
1216 (1)
1173 (6)
1130 (16)
1019 (18)
989 (6)
959 (61)
864 (5)
719 (100)
1190
1147
1113
1001
987
947
841
708
1214 (16)
1119 (16)
1085 (16)
1047 (3)
1013 (28)
966 (84)
853 (33)
695 (64)
1179
1093
1068
1029
988
948
830
688
1308 (61)
1242 (4)
1165 (76)
1037 (19)
1029 (7)
943 (27)
925 (30)
807 (100)
1281
1223
1134
1019
1006
915
911
767
20
655 (40)
653
657 (100)
645
624 (49)
618
21
532 (12)
534
602 (13)
591
574 (6)
555
22
414 (50)
404
456 (39)
452
531 (3)
529
23
305 (3)
309
359 (3)
357
357 (7)
347
24
281 (19)
284
298 (20)
294
339 (1)
349
25
264 (2)
250
240 (1)
228
233 (1)
236
26
244 (4)
229
231 (3)
201
219(1)
211
27
106 (0)
107
95 (0)
82
152 (1)
152
a
Numbers in parentheses are IR intensities normalized to the most intense line. The intensities
are 73.7 (19), 47.5 (20), and 46.6 (19) km mol1 for structures (2a), (2b), and (3), respectively.
3
Table SII. Comparison of vibrational wavenumbers (in cm1) and IR intensities of
trans-3-buten-1-yl (5a) and cis-3-buten-1-yl (5b) radicals predicted with the
B3PW91/6-311++g(2d,2p) method.
trans-3-buten-1-yl (5a)
cis-3-buten-1-yl (5b)
harmonic anharmonic
harmonic anharmonic
a
3259
(18)
3117
2
3261
(19)a
3112
1
3085
3232 (29)
3092
2 3225 (26)
3032
3157 (17)
3032
3 3152 (30)
3144
(13)
3005
3151
(17)
3015
4
2985
3139 (44)
2989
5 3136 (26)
2866
3026 (34)
2880
6 3028 (30)
2831
2931 (54)
2792
7 2962 (39)
1662
1707 (44)
1657
8 1706 (31)
1426
1468 (5)
1431
9 1461 (5)
1420
1449 (32)
1415
10 1456 (16)
1406
1433 (3)
1398
11 1441 (3)
1305
1363 (1)
1318
12 1336 (2)
1286
1328 (0)
1306
13 1318 (2)
1211
1224 (4)
1200
14 1237 (2)
1072
1132 (3)
1111
15 1115 (1)
1064
1049 (14)
1039
16 1082 (4)
1048
(6)
1029
1035
(10)
1014
17
1003
1025 (18)
1008
18 1026 (24)
946 (89)
932
946 (100)
925
19
898
(1)
881
883
(11)
860
20
800 (10)
800
829 (8)
813
21
658 (20)
650
589 (11)
587
22
498
(100)
526
537
(44)
528
23
418 (2)
428
493 (86)
524
24
321 (3)
320
281 (0)
263
25
133
(0)
87
157
(0)
145
26
101 (1)
59
143 (4)
139
27
a
Numbers in parentheses are IR intensities normalized to the most intense line. The intensities
are 51.9 (25) and 42.1 (19) km mol1 for conformers (5a) and (5b), respectively.
mode
4
FIG. S1. Geometries of (a) trans-1,3-butadien and (b) Cl2-C4H6 predicted with the
B3PW91/6-311++g(2d,2p) method. Bond distances are in Å, and angles in degrees.
FIG. S2. Relative integrated line intensities as a function of the irradiation period with light at
365 nm for (a) the Cl2-C4H6 complex at 914.5 cm1, (b) trans-1-chloromethylallyl at
809.0 cm1 and (c) 3,4-dichloro-1-butene at 738.8 cm1.
5
FIG. S1, Bahou/Wu/Tanaka/Lee
6
FIG. S2, Bahou/Wu/Tanaka/Lee
7