TY - JOUR

T1 - Solvent effects in four-component relativistic electronic structure theory based on the reference interaction-site model

AU - Kanemaru, Kodai

AU - Watanabe, Yoshihiro

AU - Yoshida, Norio

AU - Nakano, Haruyuki

N1 - Funding Information:
This work was supported by the Japan Society for the Promotion of Science (JSPS) Kakenhi (Grant Number: 21K04980 to Haruyuki Nakano, 19H02677 and 22H05089 to Norio Yoshida). Numerical calculations were partially cconducted at the Research Center for Computational Science, Institute for Molecular Science, National Institutes of Natural Sciences (Project: 22‐IMS‐C076) and using MCRP‐S at the Center for Computational Sciences, University of Tsukuba.
Funding Information:
This work was supported by the Japan Society for the Promotion of Science (JSPS) Kakenhi (Grant Number: 21K04980 to Haruyuki Nakano, 19H02677 and 22H05089 to Norio Yoshida). Numerical calculations were partially cconducted at the Research Center for Computational Science, Institute for Molecular Science, National Institutes of Natural Sciences (Project: 22-IMS-C076) and using MCRP-S at the Center for Computational Sciences, University of Tsukuba.
Publisher Copyright:
© 2022 Wiley Periodicals LLC.

PY - 2023/1/5

Y1 - 2023/1/5

N2 - A combined method of the Dirac–Hartree–Fock (DHF) method and the reference interaction-site model (RISM) theory is reported; this is the initial implementation of the coupling of the four-component relativistic electronic structure theory and an integral equation theory of molecular liquids. In the method, the DHF and RISM equations are solved self-consistently, and therefore the electronic structure of the solute, including relativistic effects, and the solvation structure are determined simultaneously. The formulation is constructed based on the variational principle with respect to the Helmholtz energy, and analytic free energy gradients are also derived using the variational property. The method is applied to the iodine ion (I−), methyl iodide (CH3I), and hydrogen chalcogenide (H2X, where X = O–Po) in aqueous solutions, and the electronic structures of the solutes, as well as the solvation free energies and their component analysis, solvent distributions, and solute–solvent interactions, are discussed.

AB - A combined method of the Dirac–Hartree–Fock (DHF) method and the reference interaction-site model (RISM) theory is reported; this is the initial implementation of the coupling of the four-component relativistic electronic structure theory and an integral equation theory of molecular liquids. In the method, the DHF and RISM equations are solved self-consistently, and therefore the electronic structure of the solute, including relativistic effects, and the solvation structure are determined simultaneously. The formulation is constructed based on the variational principle with respect to the Helmholtz energy, and analytic free energy gradients are also derived using the variational property. The method is applied to the iodine ion (I−), methyl iodide (CH3I), and hydrogen chalcogenide (H2X, where X = O–Po) in aqueous solutions, and the electronic structures of the solutes, as well as the solvation free energies and their component analysis, solvent distributions, and solute–solvent interactions, are discussed.

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U2 - 10.1002/jcc.27009

DO - 10.1002/jcc.27009

M3 - Article

C2 - 36190170

AN - SCOPUS:85139196347

SN - 0192-8651

VL - 44

SP - 5

EP - 14

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

IS - 1

ER -