Multireference Density Functional Theory for Describing Ground and Excited States with Renormalized Singles.

Journal Article (Journal Article)

We applied renormalized singles (RS) in the multireference density functional theory (DFT) to calculate accurate energies of ground and excited states. The multireference DFT approach determines the total energy of the N -electron system as the sum of the (N - 2)-electron energy from a density functional approximation (DFA) and the two-electron addition energies from the particle-particle Tamm-Dancoff approximation (ppTDA), naturally including multireference description. The ppTDA@RS-DFA approach uses the RS Hamiltonian capturing all singles contributions in calculating two-electron addition energies, and its total energy is optimized with the optimized effective potential method. It significantly improves the original ppTDA@DFA. For ground states, ppTDA@RS-DFA properly describes dissociation curves tested and the double bond rotation of ethylene. For excited states, ppTDA@RS-DFA provides accurate excitation energies and largely eliminates the DFA dependence. ppTDA@RS-DFA thus provides an efficient multireference approach to systems with static correlation.

Full Text

Duke Authors

Cited Authors

  • Li, J; Chen, Z; Yang, W

Published Date

  • January 2022

Published In

Volume / Issue

  • 13 / 3

Start / End Page

  • 894 - 903

PubMed ID

  • 35049309

Pubmed Central ID

  • PMC9365454

Electronic International Standard Serial Number (EISSN)

  • 1948-7185

International Standard Serial Number (ISSN)

  • 1948-7185

Digital Object Identifier (DOI)

  • 10.1021/acs.jpclett.1c03913

Language

  • eng