Relativistic Jahn-Teller effects in the quartet states of K3 and Rb3: a vibronic analysis of the 2 (4)E' <-- 1 (4)A2' electronic transitions based on ab initio calculations

Andreas W Hauser; Gerald Auböck; Carlo Callegari; Wolfgang E Ernst

doi:10.1063/1.3394015

Relativistic Jahn-Teller effects in the quartet states of K3 and Rb3: a vibronic analysis of the 2 (4)E' <-- 1 (4)A2' electronic transitions based on ab initio calculations

J Chem Phys. 2010 Apr 28;132(16):164310. doi: 10.1063/1.3394015.

Authors

Andreas W Hauser¹, Gerald Auböck, Carlo Callegari, Wolfgang E Ernst

Affiliation

¹ Institute of Experimental Physics, Graz University of Technology, Petersgasse 16, A-8010 Graz, Austria. andreas.w.hauser@gmail.com

PMID: 20441278
DOI: 10.1063/1.3394015

Abstract

We apply second-order multireference Rayleigh-Schrodinger perturbation theory to obtain the adiabatic potential energy surface of the 1 (4)A(2)(') lowest quartet state and the 2 (4)E(') excited state of K(3) and Rb(3). Both trimers show a typical Emultiply sign in circlee Jahn-Teller distortion in their 2 (4)E(') state, which is analyzed in terms of relativistic Jahn-Teller effect theory. Linear, quadratic, and spin-orbit coupling terms are extracted from the ab initio results and used to generate simulated spectra for a direct comparison with laser-induced fluorescence and magnetic circular dichroism spectra of alkali-doped helium nanodroplets [Aubock et al., J. Chem. Phys. 129, 114501 (2008)].