Long-range behavior of the transition dipole moments of heteronuclear dimers XY (X, Y = Li, Na, K, Rb) based on ab initio calculations

• Published in: Physical chemistry chemical physics : PCCP Vol. 20; no. 3; pp. 1889 - 1896
• Main Authors: Bormotova, E A, Kozlov, S V, Pazyuk, E A, Stolyarov, A V
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 2018
• Subjects: Configuration interaction; Dimers; Dipole moments; Electrons; Mathematical analysis; Polarization; Wave functions
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c7cp05548j

The ab initio electronic transition dipole moments (ETDMs) of heteronuclear dimers XY (X, Y = Li, Na, K, Rb) were calculated between the ground and excited states converging to the lowest three dissociation limits. The spin-allowed ETDMs were evaluated in a wide range of interatomic distances, R, by means of the quasi-relativistic electronic wave functions obtained by the multi-reference configuration interaction method. The inner-shell electrons (2 electrons for Li and Na atoms, and 10 and 28 for K and Rb, respectively) were described using the non-empirical shape-consistent effective core potentials. The l-independent core polarization potentials of each atom were used to take core-polarization and core-valence correlation effects into account. The long-range behavior of both singlet-singlet X Σ -(2,3) Σ ;(1,2) Π and triplet-triplet a Σ -(2,3) Σ ;(1,2) Π transition moments is perfectly fitted at large R-distance by the asymptotic formula of X. Chu and A. Dalgarno, Phys. Rev. A: At., Mol., Opt. Phys., 2002, 66, 024701: , where the coefficient β is equal to 2 and -1 for the Σ-Σ and Σ-Π transitions, respectively. The n S-n P transition moments, d , and dynamic polarizabilites, α , of the alkali atoms in the n S state extracted from the present molecular calculations coincide with their empirical and ab initio counterparts to within a few percent.