Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Chow, Mathew; Lambros, Eleftherios; Li, Xiaosong; Hammes-Schiffer, Sharon

doi:10.1021/acs.jctc.3c00361

Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Journal Article · Sat Jun 17 00:00:00 EDT 2023 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.3c00361· OSTI ID:2554028

Chow, Mathew ^[1]; Lambros, Eleftherios ^[2]; ^[2]; ^[1]

Yale University, New Haven, CT (United States)
University of Washington, Seattle, WA (United States)

Hybrid quantum mechanical/molecular mechanical (QM/MM) methods allow simulations of chemical reactions in atomistic solvent and heterogeneous environments such as proteins. Herein, the nuclear–electronic orbital (NEO) QM/MM approach is introduced to enable the quantization of specified nuclei, typically protons, in the QM region using a method such as NEO-density functional theory (NEO-DFT). This approach includes proton delocalization, polarization, anharmonicity, and zero-point energy in geometry optimizations and dynamics. Expressions for the energies and analytical gradients associated with the NEO-QM/MM method, as well as the previously developed polarizable continuum model (NEO-PCM), are provided. Geometry optimizations of small organic molecules hydrogen bonded to water in either dielectric continuum solvent or explicit atomistic solvent illustrate that aqueous solvation can strengthen hydrogen-bonding interactions for the systems studied, as indicated by shorter intermolecular distances at the hydrogen-bond interface. We then performed a real-time direct dynamics simulation of a phenol molecule in explicit water using the NEO-QM/MM method. Furthermore, these developments and initial examples provide the foundation for future studies of nuclear–electronic quantum dynamics in complex chemical and biological environments.

View Accepted Manuscript (DOE)

Research Organization:: Yale University, New Haven, CT (United States); University of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0023284

OSTI ID:: 2554028

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 13 Vol. 19; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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