Molecular Vibrational Frequencies with Multiple Quantum Protons within the Nuclear-Electronic Orbital Framework

Tanner Culpitt, Yang Yang, Patrick E. Schneider, Fabijan Pavošević, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


The nuclear-electronic orbital (NEO) approach treats all electrons and specified nuclei, typically protons, on the same quantum mechanical level. Proton vibrational excitations can be calculated using multicomponent time-dependent density functional theory (NEO-TDDFT) for fixed classical nuclei. Recently the NEO-DFT(V) approach was developed to enable the calculation of molecular vibrational frequencies for modes composed of both classical and quantum nuclei. This approach uses input from NEO-TDDFT to construct an extended NEO Hessian that depends on the expectation values of the quantum protons as well as the classical nuclear coordinates. Herein strategies are devised for extending these approaches to molecules with multiple quantum protons in a self-contained, effective, and computationally practical manner. The NEO-TDDFT method is shown to describe vibrational excitations corresponding to collective nuclear motions, such as linear combinations of proton vibrational excitations. The NEO-DFT(V) approach is shown to incorporate the most significant anharmonic effects in the molecular vibrations, particularly for the hydrogen stretching modes. These theoretical strategies pave the way for a wide range of multicomponent quantum chemistry applications.

Original languageEnglish (US)
Pages (from-to)6840-6849
Number of pages10
JournalJournal of Chemical Theory and Computation
Issue number12
StatePublished - Dec 10 2019
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Computer Science Applications
  • Physical and Theoretical Chemistry


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