Dynamical variational approach to non-adiabatic electronic structure

Andrei Piryatinski, Sergei Tretiak, Vladimir Y. Chernyak

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

Studying non-adiabatic effects in molecular dynamics simulations and modeling their optical signatures in linear and non-linear spectroscopies calls for electronic structure calculations in a situation when the ground state is degenerate or almost degenerate. Such degeneracy causes serious problems in invoking single Slater determinant Hartree-Fock (HF) and density functional theory (DFT) methods. To resolve this problem, we develop a generalization of time-dependent (dynamical) variational approach which accounts for the degenerate or almost degenerate ground state structure. Specifically, we propose a ground state ansatz for the subspace of generalized electronic configurations spanned on the degenerate grounds state multi-electron wavefunctions. Further employing the invariant form of Hamilton dynamics we arrive with the classical equations of motion describing the time-evolution of this subspace in the vicinity of the stationary point. The developed approach can be used for accurate calculations of molecular excited states and electronic spectra in the degenerate case.

Original languageEnglish
Pages (from-to)25-38
Number of pages14
JournalChemical Physics
Volume347
Issue number1-3
DOIs
Publication statusPublished - 23 May 2008
Externally publishedYes

Keywords

  • Degenerate ground state
  • Dynamical variational method
  • Non-adiabatic dynamics
  • Non-linear spectroscopy
  • TDDFT
  • TDHF
  • Unavoided level crossing

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