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Pseudorotational dynamics of H 3 + and Li 3 +
Author(s) -
Hagelberg F.
Publication year - 2001
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.1056
Subject(s) - excited state , anharmonicity , potential energy surface , chemistry , degenerate energy levels , ground state , pseudorotation , coupling (piping) , atomic physics , potential energy , anisotropy , adiabatic process , molecular physics , physics , molecule , quantum mechanics , engineering , organic chemistry , mechanical engineering
The origin of the pseudoprecession phenomenon is investigated through a computational study of the time evolution of H 3 + and Li 3 + by electron nuclear dynamics theory. In particular, the pseudorotation of both molecules is shown to induce a spatial rotation, which in turn leads to Coriolis coupling of the two orthogonal nuclear shape deformation modes. This effect is rooted in an anisotropy of the molecular ground state potential energy surface that is caused by the interaction between the D 3 h ground state and a twofold degenerate first excited state. Computations are performed for a variety of vibrational energies. In addition, the impact of the anharmonicity of the ground state potential surface on the shape deformation modes and the coupling between them is discussed. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001