We apply second-order multireference Rayleigh-Schrödinger perturbation theory to obtain the adiabatic potential energy surface of the 1 4A 2′ lowest quartet state and the 2 4E ′ excited state of K3 and Rb3. Both trimers show a typical Ee Jahn-Teller distortion in their 24E ′ 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 [Auböck, J. Chem. Phys. 129, 114501 (2008)].
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry