Excited-State Potential Energy Surfaces, Conical Intersections, and Analytical Gradients from Ground-State Density Functional Theory.

Journal Article (Journal Article)

Kohn-Sham density functional theory (KS-DFT) has been a well-established theoretical foundation for ground-state electronic structure and has achieved great success in practical calculations. Recently, utilizing the eigenvalues from KS or generalized KS (GKS) calculations as an approximation to the quasiparticle energies, our group demonstrated a method to calculate the excitation energies from (G)KS calculation on the ground-state ( N - 1)-electron system. This method is now called QE-DFT (quasiparticle energies from DFT). In this work, we extend this QE-DFT method to describe excited-state potential energy surfaces (PESs), conical intersections, and the analytical gradients of excited-state PESs. The analytical gradients were applied to perform geometry optimization for excited states. In conjunction with several commonly used density functional approximations, QE-DFT can yield PESs in the vicinity of the equilibrium structure with accuracy similar to that from time-dependent DFT (TD-DFT). Furthermore, it describes conical intersection well, in contrast to TD-DFT. Good results for geometry optimization, especially bond length, of low-lying excitations for 14 small molecules are presented. The capability of describing excited-state PESs, conical intersections, and analytical gradients from QE-DFT and its efficiency based on just ground-state DFT calculations should be of great interest for describing photochemical and photophysical processes in complex systems.

Full Text

Duke Authors

Cited Authors

  • Mei, Y; Yang, W

Published Date

  • May 2019

Published In

Volume / Issue

  • 10 / 10

Start / End Page

  • 2538 - 2545

PubMed ID

  • 31038964

Pubmed Central ID

  • PMC7449530

Electronic International Standard Serial Number (EISSN)

  • 1948-7185

International Standard Serial Number (ISSN)

  • 1948-7185

Digital Object Identifier (DOI)

  • 10.1021/acs.jpclett.9b00712


  • eng