Quantitative Analysis of Vibration-Rotational Spectra of Diatomic Molecules with (v,j)-Dependent Dynamical Reference Conformation. Application to LiH X1Σ+
M. Molski
Department of Theoretical Chemistry, Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland
Received: May 11, 1999
Full Text PDF
An extension of deformationally self-consistent approach to a quantitative analysis of adiabatic and nonadiabatic effects in vibration-rotational spectra of diatomic molecules is presented. We consider vibrational displacements of nuclei in the vicinity of dynamical reference conformation RvJ that depends not only on the rotational quantum number J through the action of centrifugal force, but also on the vibrational v one, through nonadiabatic vibrational effects of high order. The method is applied to LiH X1Σ+; reported wave numbers of transitions are reproduced with σ̂=1.090 and F=5.98×1014 using 14 independently adjusted parameters and 14 constrained parameters ti=0-6Li,H, representing nonadiabatic rotational effects. The latter have been evaluated from the rotational g-factor and electric dipole moment of LiH, both electronically computed.
DOI: 10.12693/APhysPolA.96.713
PACS numbers: 33.15.Mt, 33.20.Vq