Ab initio calculations of spectroscopic constants and vibrational state lifetimes of diatomic alkali-alkaline-earth cations

Dmitry A Fedorov; Dustin K Barnes; Sergey A Varganov

doi:10.1063/1.4986818

Ab initio calculations of spectroscopic constants and vibrational state lifetimes of diatomic alkali-alkaline-earth cations

J Chem Phys. 2017 Sep 28;147(12):124304. doi: 10.1063/1.4986818.

Authors

Dmitry A Fedorov¹, Dustin K Barnes¹, Sergey A Varganov¹

Affiliation

¹ Department of Chemistry, University of Nevada, Reno, 1664 N. Virginia St., Reno, Nevada 89557-0216, USA.

PMID: 28964028
DOI: 10.1063/1.4986818

Abstract

We investigate the lifetimes of vibrational states of diatomic alkali-alkaline-earth cations to determine their suitability for ultracold experiments where long decoherence time and controllability by an external electric field are desirable. The potential energy and permanent dipole moment curves for the ground electronic states of LiBe⁺, LiMg⁺, NaBe⁺, and NaMg⁺ are obtained using the coupled cluster with singles doubles and triples and multireference configuration interaction methods in combination with large all-electron cc-pCVQZ and aug-cc-pCV5Z basis sets. The energies and wave functions of all vibrational states are obtained by solving the Schrödinger equation for nuclei with the B-spline basis set method. To predict the lifetimes of vibrational states, the transition dipole moments, as well as the Einstein coefficients describing spontaneous emission, and the stimulated absorption and emission induced by black body radiation are calculated. Surprisingly, in all studied ions, the lifetimes of the highest excited vibrational states are similar to the lifetimes of the ground vibrational states indicating that highly vibrationally excited ions could be useful for the ultracold experiments requiring long decoherence time.