Characters of representations for molecular motions
Motion |
E |
4C3 |
4(C3)2 |
3C2 |
i |
4(S6)5 |
4S6 |
3σh |
Cartesian 3N |
252 |
0 |
0 |
0 |
0 |
0 |
0 |
4 |
Translation (x,y,z) |
3 |
0 |
0 |
-1 |
-3 |
0 |
0 |
1 |
Rotation (Rx,Ry,Rz) |
3 |
0 |
0 |
-1 |
3 |
0 |
0 |
-1 |
Vibration |
246 |
0 |
0 |
2 |
0 |
0 |
0 |
4 |
Decomposition to irreducible representations
Motion |
Ag |
Eg*
|
Tg |
Au |
Eu*
|
Tu |
Total |
Cartesian 3N |
11 |
11 |
31 |
10 |
10 |
32 |
105 |
Translation (x,y,z) |
0 |
0 |
0 |
0 |
0 |
1 |
1 |
Rotation (Rx,Ry,Rz) |
0 |
0 |
1 |
0 |
0 |
0 |
1 |
Vibration |
11 |
11 |
30 |
10 |
10 |
31 |
103 |
Molecular parameter
Number of Atoms (N) |
84
|
Number of internal coordinates |
246
|
Number of independant internal coordinates |
11
|
Number of vibrational modes |
103
|
Force field analysis
Allowed / forbidden vibronational transitions
Operator |
Ag |
Eg*
|
Tg |
Au |
Eu*
|
Tu |
Total |
Linear (IR) |
11 |
11 |
30 |
10 |
10 |
31 |
31 / 72 |
Quadratic (Raman) |
11 |
11 |
30 |
10 |
10 |
31 |
52 / 51 |
IR + Raman |
- - - - |
- - - - |
- - - - |
10 |
10 |
- - - - |
0* / 20 |
* Parity Mutual Exclusion Principle
Characters of force fields
(Symmetric powers of vibration representation)
Force field |
E |
4C3 |
4(C3)2 |
3C2 |
i |
4(S6)5 |
4S6 |
3σh |
linear |
246 |
0 |
0 |
2 |
0 |
0 |
0 |
4 |
quadratic |
30.381 |
0 |
0 |
125 |
123 |
0 |
0 |
131 |
cubic |
2.511.496 |
82 |
82 |
248 |
0 |
0 |
0 |
504 |
quartic |
156.340.626 |
0 |
0 |
7.874 |
7.626 |
0 |
0 |
8.626 |
quintic |
7.817.031.300 |
0 |
0 |
15.500 |
0 |
0 |
0 |
32.000 |
sextic |
327.012.476.050 |
3.403 |
3.403 |
333.250 |
317.750 |
41 |
41 |
380.750 |
Decomposition to irreducible representations
Column with number of nonvanshing force constants highlighted
Force field |
Ag |
Eg*
|
Tg |
Au |
Eu*
|
Tu |
linear |
11 |
11 |
30 |
10 |
10 |
31 |
quadratic |
1.303 |
1.303 |
3.781 |
1.260 |
1.260 |
3.783 |
cubic |
104.767 |
104.726 |
313.843 |
104.641 |
104.600 |
313.969 |
quartic |
6.516.573 |
6.516.573 |
19.541.469 |
6.513.781 |
6.513.781 |
19.541.719 |
quintic |
325.715.575 |
325.715.575 |
977.122.975 |
325.707.575 |
325.707.575 |
977.130.975 |
sextic |
13.625.623.473 |
13.625.621.751 |
40.876.509.975 |
13.625.501.779 |
13.625.500.098 |
40.876.525.725 |
Further Reading
- J.K.G. Watson, J. Mol. Spec. 41 229 (1972)
The Numbers of Structural Parameters and Potential Constants of Molecules
- X.F. Zhou, P. Pulay. J. Comp. Chem. 10 No. 7, 935-938 (1989)
Characters for Symmetric and Antisymmetric Higher Powers of Representations:
Application to the Number of Anharmonic Force Constants in Symmetrical Molecules
- F. Varga, L. Nemes, J.K.G. Watson. J. Phys. B: At. Mol. Opt. Phys. 10 No. 7, 5043-5048 (1996)
The number of anharmonic potential constants of the fullerenes C60 and C70
Contributions to nonvanishing force field constants
pos(X) : Position of irreducible representation (irrep) X in character table of T
h
Subtotal: <Number of nonvanishing force constants in subsection> / <number of nonzero irrep combinations in subsection> / <number of irrep combinations in subsection>
Total: <Number of nonvanishing force constants in force field> / <number of nonzero irrep combinations in force field> / <number of irrep combinations in force field>
Contributions to nonvanishing quadratic force field constants
Irrep combinations (i,i) with indices: pos(Ag) ≤ i ≤ pos(Tu) |
..66. |
AgAg. | ..121. |
EgEg. | ..465. |
TgTg. | ..55. |
AuAu. | ..100. |
EuEu. | ..496. |
TuTu. | | |
| |
| |
| |
Subtotal: 1.303 / 6 / 6 |
Irrep combinations (i,j) with indices: pos(Ag) ≤ i ≤ j ≤ pos(Tu) |
Subtotal: 0 / 0 / 15 |
Total: 1.303 / 6 / 21 |
Contributions to nonvanishing cubic force field constants
Irrep combinations (i,i,i) with indices: pos(Ag) ≤ i ≤ pos(Tu) |
..286. |
AgAgAg. | ..572. |
EgEgEg. | ..9.020. |
TgTgTg. | | |
| |
| |
| |
| |
| |
| |
Subtotal: 9.878 / 3 / 6 |
Irrep combinations (i,i,j) (i,j,j) with indices: pos(Ag) ≤ i ≤ j ≤ pos(Tu) |
..1.331. |
AgEgEg. | ..5.115. |
AgTgTg. | ..605. |
AgAuAu. | ..1.100. |
AgEuEu. | ..5.456. |
AgTuTu. | ..10.230. |
EgTgTg. | ..1.210. |
EgEuEu. | ..10.912. |
EgTuTu. | ..28.830. |
TgTuTu. | | |
Subtotal: 64.789 / 9 / 30 |
Irrep combinations (i,j,k) with indices: pos(Ag) ≤ i ≤ j ≤ k ≤ pos(Tu) |
..2.200. |
EgAuEu. | ..9.300. |
TgAuTu. | ..18.600. |
TgEuTu. | | |
| |
| |
| |
| |
| |
| |
Subtotal: 30.100 / 3 / 20 |
Total: 104.767 / 15 / 56 |
Contributions to nonvanishing quartic force field constants
Irrep combinations (i,i,i,i) with indices: pos(Ag) ≤ i ≤ pos(Tu) |
..1.001. |
AgAgAgAg. | ..4.356. |
EgEgEgEg. | ..257.145. |
TgTgTgTg. | ..715. |
AuAuAuAu. | ..3.025. |
EuEuEuEu. | ..292.392. |
TuTuTuTu. | | |
| |
| |
| |
Subtotal: 558.634 / 6 / 6 |
Irrep combinations (i,i,i,j) (i,j,j,j) with indices: pos(Ag) ≤ i ≤ j ≤ pos(Tu) |
..6.292. |
AgEgEgEg. | ..99.220. |
AgTgTgTg. | ..197.780. |
EgTgTgTg. | ..4.400. |
AuEuEuEu. | ..99.510. |
AuTuTuTu. | ..198.400. |
EuTuTuTu. | | |
| |
| |
| |
Subtotal: 605.602 / 6 / 30 |
Irrep combinations (i,i,j,j) with indices: pos(Ag) ≤ i ≤ j ≤ pos(Tu) |
..7.986. |
AgAgEgEg. | ..30.690. |
AgAgTgTg. | ..3.630. |
AgAgAuAu. | ..6.600. |
AgAgEuEu. | ..32.736. |
AgAgTuTu. | ..117.645. |
EgEgTgTg. | ..6.655. |
EgEgAuAu. | ..19.360. |
EgEgEuEu. | ..125.488. |
EgEgTuTu. | ..25.575. |
TgTgAuAu. |
..97.650. |
TgTgEuEu. | ..1.556.820. |
TgTgTuTu. | ..5.500. |
AuAuEuEu. | ..27.280. |
AuAuTuTu. | ..104.160. |
EuEuTuTu. | | |
| |
| |
| |
| |
Subtotal: 2.167.775 / 15 / 15 |
Irrep combinations (i,i,j,k) (i,j,j,k) (i,j,k,k) with indices: pos(Ag) ≤ i ≤ j ≤ k ≤ pos(Tu) |
..13.200. |
EgEgAuEu. | ..93.000. |
TgTgAuEu. | ..279.000. |
TgTgAuTu. | ..558.000. |
TgTgEuTu. | ..112.530. |
AgEgTgTg. | ..13.310. |
AgEgEuEu. | ..120.032. |
AgEgTuTu. | ..317.130. |
AgTgTuTu. | ..634.260. |
EgTgTuTu. | ..99.200. |
AuEuTuTu. |
Subtotal: 2.239.662 / 10 / 60 |
Irrep combinations (i,j,k,l) with indices: pos(Ag) ≤ i ≤ j ≤ k ≤ l ≤ pos(Tu) |
..24.200. |
AgEgAuEu. | ..102.300. |
AgTgAuTu. | ..204.600. |
AgTgEuTu. | ..204.600. |
EgTgAuTu. | ..409.200. |
EgTgEuTu. | | |
| |
| |
| |
| |
Subtotal: 944.900 / 5 / 15 |
Total: 6.516.573 / 42 / 126 |
Calculate contributions to
Last update November, 13th 2023 by A. Gelessus, Impressum, Datenschutzerklärung/DataPrivacyStatement