Generalized Nuclear-Electronic Orbital Multistate Density Functional Theory for Multiple Proton Transfer Processes

Joseph A. Dickinson, Qi Yu, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Proton transfer and hydrogen tunneling play pivotal roles in many chemical and biological processes. The nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) approach was developed to describe hydrogen tunneling systems within the multicomponent NEO framework, where the transferring proton is quantized and treated with molecular orbital techniques on the same level as the electrons. Herein, the NEO-MSDFT framework is generalized to an arbitrary number of quantum protons to allow applications to systems involving the transfer and tunneling of multiple protons. The generalized NEO-MSDFT approach is shown to produce delocalized, bilobal proton densities and accurate tunneling splittings for fixed geometries of the formic acid dimer and asymmetric substituted variants, as well as the porphycene molecule. Investigation of a protonated water chain highlights the applicability of this approach to proton relay systems. This work provides the foundation for nuclear-electronic quantum dynamics simulations of a wide range of multiple proton transfer processes.

Original languageEnglish (US)
Pages (from-to)6170-6178
Number of pages9
JournalJournal of Physical Chemistry Letters
Volume14
Issue number26
DOIs
StatePublished - Jul 6 2023
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry

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