TY - JOUR
T1 - Molecular Vibrational Frequencies with Multiple Quantum Protons within the Nuclear-Electronic Orbital Framework
AU - Culpitt, Tanner
AU - Yang, Yang
AU - Schneider, Patrick E.
AU - Pavošević, Fabijan
AU - Hammes-Schiffer, Sharon
N1 - Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/12/10
Y1 - 2019/12/10
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.jctc.9b00665
DO - 10.1021/acs.jctc.9b00665
M3 - Article
C2 - 31618582
AN - SCOPUS:85074663280
SN - 1549-9618
VL - 15
SP - 6840
EP - 6849
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 12
ER -