Abstract
The structure and the conformational behavior of the chloral CCl3CHO molecule in the lowest excited singlet state (S1) was investigated by CASSCF and CI ab initio quantum-chemical methods. It is shown that electronic excitation S1←S0 causes significant changes in the molecular structure, namely, CCl3 top rotation and “pyramidalization” of the carbonyl (CCHO) fragment. A relationship between the torsional and inversion vibrations of chloral in the S1 state has been found. For large-amplitude nuclear motions corresponding to the torsional and inversion vibrations, the corresponding one- and two-dimensional problems were solved. The results are compared with the experimental data and with the results of previous calculations for the lowest excited triplet (T1) state.
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References
I. A. Godunov and N. N. Yakovlev, Zh. Strukt. Khim., 36, No. 2, 269-285 (1995).
I. A. Godunov, N. N. Yakovlev, and E. B. Averina, Izv. Ross. Akad. Nauk, Ser. Khim., No. 2, 294-299 (1998).
I. A. Godunov and N. N. Yakovlev, Zh. Fiz. Khim., 72, 1087-1091 (1998).
N. N. Yakovlev, M. N. Mikhailov, and I. A. Godunov, Zh. Strukt. Khim., 39, 507-513 (1998).
V. A. Bataev, M. N. Mikhailov, A. V. Abramenkov, et al., ibid., 42, 69-79 (2001).
V. A. Bataev, V. I. Pupyshev, A. V. Abramenkov, and I. A. Godunov, Russ. J. Phys. Chem., 74, Suppl. 2, 279-291 (2000).
W. J. Stevens, H. Bash, and M. Krauss, J. Chem. Phys., 81, 6026-6033 (1984).
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, et al., J. Comput. Chem., 14, 1347-1363 (1993).
A. A. Granovsky, http: //classic.chem.msu.su/gran/gamess/index.html.
T. H. Dunning Jr. and P. J. Hay, Methods of Electronic Structure Theory, Ch. 1, H. F. Schaefer III (ed.), Plenum, New York (1977), pp. 1-27.
G. Hagen, Acta Chem. Scand., 25, 813-832 (1971).
V. A. Bataev, A. V. Abramenkov, V. I. Pupyshev, and I. A. Godunov, Zh. Fiz. Khim., 74, 1929-1937 (2000).
H. Liu, E. C. Lim, C. Munos-Caro, et al., J. Chem. Phys., 105, 2547-2552 (1996).
A. Nino, C. Munos-Caro, and D. C. Moule, J. Phys. Chem., 98, 1519-1524 (1994).
A. V. Abramenkov, Zh. Fiz. Khim., 69, 1048-1052 (1995).
I. A. Godunov, A. V. Abramenkov, and N. N. Yakovlev, Zh. Strukt. Khim., 39, No. 5, 947-961 (1998).
P. R. Bunker, Molecular Symmetry and Spectroscopy, Academic Press, New York (1979).
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Bataev, V.A., Mikhailov, M.N., Abramenkov, A.V. et al. Molecular Structure of Chloral (CCl3CHO) in the Lowest Excited Singlet State. Journal of Structural Chemistry 42, 723–729 (2001). https://doi.org/10.1023/A:1017905030145
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DOI: https://doi.org/10.1023/A:1017905030145