Nuclear-Electronic Orbital Time-Dependent Configuration Interaction Method

Scott M. Garner, Shiv Upadhyay, Xiaosong Li, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

Abstract

Combining real-time electronic structure with the nuclear-electronic orbital (NEO) method has enabled the simulation of complex nonadiabatic chemical processes. However, accurate descriptions of hydrogen tunneling and double excitations require multiconfigurational treatments. Herein, we develop and implement the real-time NEO time-dependent configuration interaction (NEO-TDCI) approach. Comparison to NEO-full CI calculations of absorption spectra for a molecular system shows that the NEO-TDCI approach can accurately capture the tunneling splitting associated with the electronic ground state as well as vibronic progressions corresponding to double electron-proton excitations associated with excited electronic states. Both of these features are absent from spectra obtained with single reference real-time NEO methods. Our simulations of hydrogen tunneling dynamics illustrate the oscillation of the proton density from one side to the other via a delocalized, bilobal proton wave function. These results indicate that the NEO-TDCI approach is highly suitable for studying hydrogen tunneling and other inherently multiconfigurational systems.

Original languageEnglish (US)
Pages (from-to)6017-6023
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume15
Issue number23
DOIs
StatePublished - Jun 13 2024

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry

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