Theoretical Studies of Dynamic Interactions in Excited States of Hydrogen-Bonded Systems
Table 3
Calculated vibrational frequencies for S1 state of benzoic acid dimer at the CIS/6-311++G(d,p) level (, stretching; , in-plane bending; , out-of-plane bending; , torsion).
No.
Sym.
Freq. (cm−1)
Approximate description
1
A′′
16
“Butterfly” monomers twisting
2
A′′
30
Oop. monomers twisting
3
A′
45
Ip. monomers twisting (“cogwheel”)
4
A′′
52
Oop. monomers rocking
5
A′′
71
(COOH)
6
A′′
80
(COOH)
7
A′
87
Ip monomers rocking (H-bond shearing)
8
A′
96
H-Bonds stretching
9
A′′
103
(COOH)
10
A′′
172
(–COOH) (A)
11
A′
214
(–COOH) (B)
12
A′′
215
(–COOH) (B)
13
A′
249
(–COOH) (A)
14
A′′
306
Oop. ring deform. (B)
15
A′
307
Ip. ring deform. (B)
16
A′′
327
Oop. asym. rings deform.
17
A′
380
Ip. ring deform. (A)
18
A′
402
Ip. ring deform. (B)
19
A′′
409
Oop. ring deform. (A)
20
A′′
437
Oop. ring deform. (A)
21
A′
497
(C–COOH) (A)
22
A′
525
(C–COOH) (B)
23
A′
592
(COOH) sciss. + ip. ring deform. (B)
24
A′
606
Ip. ring deform. (A)
25
A′′
624
(CH) (B)
26
A′
646
(COOH) sciss. + ip. ring deform. (A)
27
A′′
673
Oop. ring deform. (A)
28
A′′
700
(COOH) + (CH) (B)
29
A′′
718
(CH) (A)
30
A′
740
(COOH) sciss. + ring breath. (B)
31
A′′
746
(OH) + (CH) (B)
32
A′′
755
(OH) + (CH) (B)
33
A′
777
(COOH) sciss. + ring breath. (A)
34
A′′
780
(C–COOH) + (OH) + (CH) (B)
35
A′′
816
(C–COOH) + (OH) + (CH) (A)
36
A′′
836
(CC) + (CH) (B)
37
A′′
860
(CC) + (CH) (A)
38
A′′
877
(OH) (A)
39
A′′
901
(OH) (B)
40
A′
903
(CC)ring (B)
41
A′
944
Ring breath. (B)
42
A′
965
(CC)ring (B)
43
A′′
965
(CH)
44
A′
976
Ring breath. (A)
45
A′
1003
Ring breath. (A)
46
A′′
1004
A(CH) (A)
47
A′′
1009
A(CH) (A)
48
A′
1021
(CC)ring (B)
49
A′
1050
(CC)ring (A)
50
A′
1089
(CC)ring + (CH) (A)
51
A′
1099
(CC)ring + (CH) (B)
52
A′
1111
(CC)ring + (CH) (A)
53
A′
1133
(CH) (B)
54
A′
1155
(CH) (A)
55
A′
1201
(CC)ring + (CH) (A)
56
A′
1205
(CC)ring + (CH) (B)
57
A′
1254
(OH) (B)
58
A′
1282
(OH) (A)
59
A′
1309
(CH) (B)
60
A′
1312
(CH) (A)
61
A′
1385
(CH) (B)
62
A′
1392
(CH) ()
63
A′
1417
(CH) ()
64
A′
1437
(CC)ring + (CH) (A)
65
A′
1445
(CC)ring + (CH) (B)
66
A′
1485
(CC)ring + (CH) (A)
67
A′
1533
(CC)ring + (CH) (B)
68
A′
1586
(CC)ring (B)
69
A′
1587
(CC)ring (A)
70
A′
1609
(CC)ring (A)
71
A′
1653
(C=O) (B)
72
A′
1723
(C=O) (A)
73
A′
2990
(CH) (A)
74
A′
3004
(CH) (A)
75
A′
3013
(CH) (A)
76
A′
3015
(CH) (B)
77
A′
3020
(CH) (B)
78
A′
3034
(CH) (A)
79
A′
3038
(CH) (A)
80
A′
3039
(CH) (B)
81
A′
3047
(CH) (B)
82
A′
3051
(CH) (B)
83
A′
3367
(OH) (A)
84
A′
3473
(OH) (B)
The calculated frequencies were uniformly scaled by a factor of 0.9. (A) and (B) label the molecule of the dimer, which is necessary for proper mode description.
