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Molecular Structure of Chloral (CCl3CHO) in the Lowest Excited Singlet State

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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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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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