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Nonadiabatic hamiltonian for electronic–vibrational coupling
Author(s) -
Kresin Vladimir Z.,
Lester William A.
Publication year - 2009
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.560360805
Subject(s) - hamiltonian (control theory) , adiabatic process , raman scattering , vibronic coupling , vibrational energy , adiabatic theorem , coupling (piping) , chemistry , molecular vibration , raman spectroscopy , scattering , atomic physics , quantum mechanics , physics , molecule , materials science , mathematics , mathematical optimization , metallurgy
A new version of adiabatic theory enabling one to evaluate higher‐order nonadiabatic terms has been developed. One introduces a nonadiabatic Hamiltonian Ĥ na so that the total Hamiltonian is given by Ĥ = Ĥ 0 + Ĥ na , where Ĥ 0 describes the noninteracting electronic and nuclear subsystems, and Ĥ na describes the electronic‐vibrational coupling. The correction to the total energy is calculated. The theory is applied to vibrational Raman scattering of aromatic molecules. Nonadiabaticity is found to play a key role in vibrational Raman scattering.