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Title: Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis set without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.
Authors:
 [1] ; ;  [2] ;  [3]
  1. College of Chemistry, Sichuan University, Chengdu 610064 (China)
  2. Key Laboratory of Chemical Laser, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)
  3. Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610064 (China)
Publication Date:
OSTI Identifier:
22415628
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 14; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ATOMIC NUMBER; ATOMS; ELECTRONS; EQUATIONS OF MOTION; EXCITATION; IONIZATION POTENTIAL; L-S COUPLING; MOLECULES; POTENTIALS; STABILIZATION; SYMMETRY; T INVARIANCE