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Some symmetry aspects of the local‐mode description of vibrational structure
Author(s) -
Gelbart William M.,
Stannard Paul R.,
Elert Mark L.
Publication year - 1978
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.560140516
Subject(s) - anharmonicity , excited state , hamiltonian (control theory) , molecular vibration , normal coordinates , symmetry (geometry) , dissociation (chemistry) , normal mode , hot band , local symmetry , vibrational partition function , molecular symmetry , chemistry , physics , molecular physics , quantum mechanics , molecule , vibration , mathematics , geometry , mathematical optimization
In the local‐mode description of vibrational structure, the nuclear coordinates—unlike the usual normal coordinates—do not reflect the molecular symmetry. Accordingly, the local‐mode product wave functions must be symmetry adapted. We discuss this simple procedure in light of its implications for the localization of vibrational energy and the dissociation limits of molecular excited states. These properties are in turn related to the separability of the total nuclear Hamiltonian and to the different ways in which the vibrational anharmonicity is “absorbed” by the local and normal coordinates.