Nonadiabatic couplings from a variational excited state method based on constrained DFT

Pablo Ramos, Michele Pavanello

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Excited Costrained Density Functional Theory (XCDFT) [Ramos and Pavanello, J. Chem. Phys. 148, 144103 (2018)] is a variational excited state method that extends ground state DFT to the computation of low-lying excited states. It borrows much of the machinery of Constrained DFT (CDFT) with a crucial difference: the constraint imposes a population of one electron in the Hilbert space spanned by the virtuals of a reference ground state. In this work, we present theory and implementation for evaluating nonadiabatic coupling vectors (NACVs) between the first excited state computed with XCDFT and the ground state. Our NACVs are computed analytically using density functional perturbation theory with a formalism that is general enough that could be applied to CDFT diabatic states. We showcase the new method with pilot NACV calculations for the conical intersection in H3, the avoided crossing in selenoacrolein, and the NACV magnitudes in azobenzene. Despite complications from the nonorthogonality of the wavefunctions, XCDFT's energy surfaces and NACVs reproduce benchmark values and respect known sum rules within a reasonable degree. This shows that XCDFT is a viable method for nonadiabatic dynamics simulations.

Original languageEnglish (US)
Article number014110
JournalJournal of Chemical Physics
Volume154
Issue number1
DOIs
StatePublished - Jan 7 2021

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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