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Title: Ab initio study of the RbSr electronic structure: Potential energy curves, transition dipole moments, and permanent electric dipole moments

Excited states and the ground state of the diatomic molecule RbSr were calculated by post Hartree-Fock molecular orbital theory up to 22 000 cm{sup −1}. We applied a multireference configuration interaction calculation based on multiconfigurational self-consistent field wave functions. Both methods made use of effective core potentials and core polarization potentials. Potential energy curves, transition dipole moments, and permanent electric dipole moments were determined for RbSr and could be compared with other recent calculations. We found a good agreement with experimental spectra, which have been obtained recently by helium nanodroplet isolation spectroscopy. For the lowest two asymptotes (Rb (5s {sup 2}S) + Sr (5s4d {sup 3}P°) and Rb (5p {sup 2}P°) + Sr (5s{sup 2} {sup 1}S)), which exhibit a significant spin-orbit coupling, we included relativistic effects by two approaches, one applying the Breit-Pauli Hamiltonian to the multireference configuration interaction wave functions, the other combining a spin-orbit Hamiltonian and multireference configuration interaction potential energy curves. Using the results for the relativistic potential energy curves that correspond to the Rb (5s {sup 2}S) + Sr (5s4d {sup 3}P°) asymptote, we have simulated dispersed fluorescence spectra as they were recently measured in our lab. The comparison with experimental data allows to benchmark bothmore » methods and demonstrate that spin-orbit coupling has to be included for the lowest states of RbSr.« less
Authors:
; ; ;  [1]
  1. Institute of Experimental Physics, Graz University of Technology, Petersgasse 16, A-8010 Graz (Austria)
Publication Date:
OSTI Identifier:
22413339
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 23; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CONFIGURATION INTERACTION; ELECTRIC DIPOLE MOMENTS; ELECTRONIC STRUCTURE; EXCITED STATES; FLUORESCENCE SPECTROSCOPY; GROUND STATES; HAMILTONIANS; HARTREE-FOCK METHOD; HELIUM; L-S COUPLING; MOLECULAR ORBITAL METHOD; POLARIZATION; POTENTIAL ENERGY; SIMULATION; SPECTRA; SPIN; WAVE FUNCTIONS