A Jahn-Teller analysis of K-3 and Rb-3 in the electronic states 1(2)E ' and 1(2)E ''

作者：Hauser Andreas W^*; Callegari Carlo; Soldan Pavel; Ernst Wolfgang E

来源：Chemical Physics, 2010, 375(1): 73-84.

DOI：10.1016/j.chemphys.2010.07.025

• Ab initio calculations
• CASSCF
• MULTI
• CASPT2
• RS2C
• Potassium
• Rubidium
• Alkali trimer
• Jahn-Teller
• Anharmonicity
• Spin-orbit

The potential energy surfaces (PES) of the Jahn-Teller distorted doublet 1(2)E' (1B(2)/1A(1)) ground state and 1(2)E '' (2B(1)/1A(2)) excited state of alkali metal trimers (K-3, Rb-3) are studied with three high-level computational chemistry methods whose results are compared: single-reference coupled cluster, equation-of-motion coupled cluster and multi-reference second-order Rayleigh-Schrodinger perturbation theory. The doubly degenerate E electronic state interacts with the twofold degenerate vibrational e mode. We use the E circle times e Jahn-Teller effect theory to analyze in detail one-and two-dimensional cuts of the PES as a function of the symmetry-adapted internal coordinates Q(s), Q(x) and Q(y) and we extract the associated Jahn-Teller parameters. Spin-orbit coupling is accounted for by means of the Effective-Core-Potential-LS technique and spin-orbit splitting constants are extracted. We also provide the geometries, the binding energies and tentative vibronic spectra for the 1(2)E '' <- 1(2)E' transitions.

• 出版日期2010-9-14