Multicomponent Density Functional Theory: Impact of Nuclear Quantum Effects on Proton Affinities and Geometries

Kurt R. Brorsen, Yang Yang, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

89 Scopus citations


Nuclear quantum effects such as zero point energy play a critical role in computational chemistry and often are included as energetic corrections following geometry optimizations. The nuclear-electronic orbital (NEO) multicomponent density functional theory (DFT) method treats select nuclei, typically protons, quantum mechanically on the same level as the electrons. Electron-proton correlation is highly significant, and inadequate treatments lead to highly overlocalized nuclear densities. A recently developed electron-proton correlation functional, epc17, has been shown to provide accurate nuclear densities for molecular systems. Herein, the NEO-DFT/epc17 method is used to compute the proton affinities for a set of molecules and to examine the role of nuclear quantum effects on the equilibrium geometry of FHF-. The agreement of the computed results with experimental and benchmark values demonstrates the promise of this approach for including nuclear quantum effects in calculations of proton affinities, pKa's, optimized geometries, and reaction paths.

Original languageEnglish (US)
Pages (from-to)3488-3493
Number of pages6
JournalJournal of Physical Chemistry Letters
Issue number15
StatePublished - Aug 3 2017
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry


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