J Phys Chem A. 2014 Sep 25;118(38):8828-41. doi: 10.1021/jp5043427. Epub 2014 Sep 16.

Theoretical study of the CsNa molecule: adiabatic and diabatic potential energy and dipole moment.

The journal of physical chemistry. A

N Mabrouk, H Berriche

PMID: 25058020 DOI: 10.1021/jp5043427

Abstract

The adiabatic and diabatic potential energy curves of the low-lying electronic states of the NaCs molecule dissociating into Na (3s, 3p) + Cs (6s, 6p, 5d, 7s, 7p, 6d, 8s, 4f) have been investigated. The molecular calculations are performed using an ab initio approach based on nonempirical pseudopotential, parametrized l-dependent polarization potentials and full configuration interaction calculations through the CIPCI quantum chemistry package. The derived spectroscopic constants (Re, De, Te, ωe, ωexe, and Be) of the ground state and lower excited states are compared with the available theoretical and experimental works. Moreover, accurate permanent and transition dipole moment have been determined as a function of the internuclear distance. The adiabatic permanent dipole moment for the first nine (1)Σ(+) electronic states have shown both ionic characters associated with electron transfer related to Cs(+)Na(-) and Cs(-)Na(+) arrangements. By a simple rotation, the diabatic permanent dipole moment is determined and has revealed a linear behavior, particularly at intermediate and large distances. Many peaks around the avoided crossing locations have been observed for the transition dipole moment between neighbor electronic states.

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• Journal Article