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Title: First-order nonadiabatic coupling matrix elements between excited states: A Lagrangian formulation at the CIS, RPA, TD-HF, and TD-DFT levels

Analytic expressions for the first-order nonadiabatic coupling matrix elements between electronically excited states are first formulated exactly via both time-independent equation of motion and time-dependent response theory, and are then approximated at the configuration interaction singles, particle-hole/particle-particle random phase approximation, and time-dependent density functional theory/Hartree-Fock levels of theory. Note that, to get the Pulay terms arising from the derivatives of basis functions, the standard response theory designed for electronic perturbations has to be extended to nuclear derivatives. The results are further recast into a Lagrangian form that is similar to that for excited-state energy gradients and allows to use atomic orbital based direct algorithms for large molecules.
Authors:
;  [1]
  1. Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, and Center for Computational Science and Engineering, Peking University, Beijing 100871 (China)
Publication Date:
OSTI Identifier:
22308984
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 1; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COUPLING; DENSITY FUNCTIONAL METHOD; EQUATIONS OF MOTION; EXCITED STATES; HARTREE-FOCK METHOD; LAGRANGIAN FUNCTION; MATRIX ELEMENTS; MOLECULES; PARTICLES; RANDOM PHASE APPROXIMATION; TIME DEPENDENCE