Is it worthwhile to go beyond the local-density approximation in subsystem density functional theory?

Stephanie A. Grimmel, Tiago Q. Teodoro, Lucas Visscher*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Frozen density embedding (FDE) theory is one of the major techniques aiming to bring modeling of extended chemical systems into the realm of high accuracy calculations. To improve its accuracy it is of interest to develop kinetic energy density functional approximations specifically for FDE applications. In the study reported here we focused on optimizing parameters of a generalized gradient approximation-like kinetic energy functional with the purpose of better describing electron excitation energies. We found that our optimized parametrizations, named excPBE and excPBE-3 (as these are derived from a Perdew-Burke-Ernzerhof-like parametrization), could not yield improvements over available functionals when applied on a test set of systems designed to probe solvatochromic shifts. Moreover, as several different functionals yielded very similar errors to the simple local-density approximation (LDA), it is questionable whether it is worthwhile to go beyond the LDA in this context.

Original languageEnglish
Article numbere26111
Pages (from-to)1-11
Number of pages11
JournalInternational Journal of Quantum Chemistry
Volume120
Issue number21
Early online date11 Dec 2019
DOIs
Publication statusPublished - 1 Nov 2020

Keywords

  • density functional theory
  • kinetic functionals
  • optimization
  • subsystem

Fingerprint Dive into the research topics of 'Is it worthwhile to go beyond the local-density approximation in subsystem density functional theory?'. Together they form a unique fingerprint.

Cite this