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Published in

Elsevier, Chemical Physics Letters, 4-6(501), p. 575-579, 2011

DOI: 10.1016/j.cplett.2010.11.047

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Separation of motions of atomic cores and valence electrons in molecules

Journal article published in 2011 by José R. Mohallem, Leonardo G. Diniz ORCID, Adriano S. Dutra
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

We perform a semi-empirical separation of the movements of cores and valence electrons in a molecule, generating coupled equations for the movement of the cores. Far from critical points of the PES, the adiabatic correction depends just on the valence wavefunction. Nonadiabatic effects turn dependent on the valence wavefunctions as well and can be evaluated by replacing the nuclear reduced mass by another one lying between the nuclear and the atomic reduced masses. A formula for the effective core mass based on electron atomic populations is introduced. Nonadiabatic corrections to vibrational levels of LiH are reported.