Many model potential energy surfaces (PESs) have been reported for water; however, none are strictly from "first-principles". Here we report such a potential, based on a many-body representation at the CCSD(T) level of theory up to the four-body interaction. The new PES is benchmarked for the isomers of the water hexamer for dissociation energies, harmonic frequencies, and unrestricted diffusion Monte Carlo (DMC) calculations of the zero-point energies of the Prism, Book, and Cage isomers. Dissociation energies of several isomers of the 20-mer agree well with recent benchmark energies. Exploratory DMC calculations on this cluster verify the robustness of the new PES for quantum simulations. The accuracy and speed of the new PES are demonstrated for standard condensed phase properties, i.e., the radial distribution function and the self-diffusion constant. Quantum effects are shown to be substantial for these observables and also needed to bring theory into excellent agreement with experiment.

q-AQUA: A Many-Body CCSD(T) Water Potential, Including Four-Body Interactions, Demonstrates the Quantum Nature of Water from Clusters to the Liquid Phase / Q. Yu, C. Qu, P.L. Houston, R. Conte, A. Nandi, J.M. Bowman. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 13:22(2022), pp. 5068-5074. [10.1021/acs.jpclett.2c00966]

q-AQUA: A Many-Body CCSD(T) Water Potential, Including Four-Body Interactions, Demonstrates the Quantum Nature of Water from Clusters to the Liquid Phase

R. Conte
;
2022

Abstract

Many model potential energy surfaces (PESs) have been reported for water; however, none are strictly from "first-principles". Here we report such a potential, based on a many-body representation at the CCSD(T) level of theory up to the four-body interaction. The new PES is benchmarked for the isomers of the water hexamer for dissociation energies, harmonic frequencies, and unrestricted diffusion Monte Carlo (DMC) calculations of the zero-point energies of the Prism, Book, and Cage isomers. Dissociation energies of several isomers of the 20-mer agree well with recent benchmark energies. Exploratory DMC calculations on this cluster verify the robustness of the new PES for quantum simulations. The accuracy and speed of the new PES are demonstrated for standard condensed phase properties, i.e., the radial distribution function and the self-diffusion constant. Quantum effects are shown to be substantial for these observables and also needed to bring theory into excellent agreement with experiment.
Settore CHIM/02 - Chimica Fisica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/930247
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