U.S. Department of Energy Office of Scientific and Technical Information
Assessing Implicit and Explicit Polarizable Solvation Models for Nuclear–Electronic Orbital Systems: Quantum Proton Polarization and Solvation Energetics
Journal Article·· Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Accurate simulations of many chemical processes require the inclusion of both nuclear quantum effects and a solvent environment. The nuclear–electronic orbital (NEO) approach, which treats electrons and select nuclei quantum mechanically on the same level, combined with a polarizable continuum model (PCM) for the solvent environment, addresses this challenge in a computationally practical manner. In this work, the NEO-PCM approach is extended beyond the IEF-PCM (integral equation formalism PCM) and C-PCM (conductor PCM) approaches to the SS(V)PE (surface and simulation of volume polarization for electrostatics) and ddCOSMO (domain decomposed conductor-like screening model) approaches. IEF-PCM, SS(V)PE, C-PCM, and ddCOSMO all exhibit similar solvation energies as well as comparable nuclear polarization within the NEO framework. The calculations show that the nuclear density does not leak out of the molecular cavity because it is much more localized than the electronic density. Finally, the polarization of quantized protons is analyzed in both continuum solvent and explicit solvent environments described by the polarizable MB-pol model, illustrating the impact of specific hydrogen-bonding interactions captured only by explicit solvation. Furthermore, these calculations highlight the relationship among solvation formalism, nuclear polarization, and energetics.
Lambros, Eleftherios, et al. "Assessing Implicit and Explicit Polarizable Solvation Models for Nuclear–Electronic Orbital Systems: Quantum Proton Polarization and Solvation Energetics." Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, vol. 127, no. 44, Oct. 2023. https://doi.org/10.1021/acs.jpca.3c03153
Lambros, Eleftherios, Link, Benjamin, Chow, Mathew, et al., "Assessing Implicit and Explicit Polarizable Solvation Models for Nuclear–Electronic Orbital Systems: Quantum Proton Polarization and Solvation Energetics," Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 127, no. 44 (2023), https://doi.org/10.1021/acs.jpca.3c03153
@article{osti_2554035,
author = {Lambros, Eleftherios and Link, Benjamin and Chow, Mathew and Lipparini, Filippo and Hammes-Schiffer, Sharon and Li, Xiaosong},
title = {Assessing Implicit and Explicit Polarizable Solvation Models for Nuclear–Electronic Orbital Systems: Quantum Proton Polarization and Solvation Energetics},
annote = {Accurate simulations of many chemical processes require the inclusion of both nuclear quantum effects and a solvent environment. The nuclear–electronic orbital (NEO) approach, which treats electrons and select nuclei quantum mechanically on the same level, combined with a polarizable continuum model (PCM) for the solvent environment, addresses this challenge in a computationally practical manner. In this work, the NEO-PCM approach is extended beyond the IEF-PCM (integral equation formalism PCM) and C-PCM (conductor PCM) approaches to the SS(V)PE (surface and simulation of volume polarization for electrostatics) and ddCOSMO (domain decomposed conductor-like screening model) approaches. IEF-PCM, SS(V)PE, C-PCM, and ddCOSMO all exhibit similar solvation energies as well as comparable nuclear polarization within the NEO framework. The calculations show that the nuclear density does not leak out of the molecular cavity because it is much more localized than the electronic density. Finally, the polarization of quantized protons is analyzed in both continuum solvent and explicit solvent environments described by the polarizable MB-pol model, illustrating the impact of specific hydrogen-bonding interactions captured only by explicit solvation. Furthermore, these calculations highlight the relationship among solvation formalism, nuclear polarization, and energetics.},
doi = {10.1021/acs.jpca.3c03153},
url = {https://www.osti.gov/biblio/2554035},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {ISSN 1089-5639},
number = {44},
volume = {127},
place = {United States},
publisher = {American Chemical Society},
year = {2023},
month = {10}}
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:
2554035
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 44 Vol. 127; ISSN 1089-5639