Diffusion theory of molecular liquids in the energy representation and application to solvation dynamics

Okita, Kazuya; Kasahara, Kento; Matubayasi, Nobuyuki

Journal of Chemical Physics, 2022, 157(24), 244505

Number of Access:559（2025-08-29 04:10 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/97734

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Title
Diffusion theory of molecular liquids in the energy representation and application to solvation dynamics
Creator
CreatorName
Okita, Kazuya
NRID
1000010824469 1000010824469
ORCID
0000-0001-7138-250X 0000-0001-7138-250X
researchmap permalink
kasakento kasakento
Scopus Author ID
56245700800 56245700800
CreatorName
Kasahara, Kento
NRID
1000020281107 1000020281107
ORCID
0000-0001-7176-441X 0000-0001-7176-441X
researchmap permalink
nbyk_MTBYS nbyk_MTBYS
Scopus Author ID
7003410578 7003410578
CreatorName
Matubayasi, Nobuyuki
Description
Okita K., Kasahara K., Matubayasi N.. Journal of Chemical Physics 157, 244505 (2022) https://doi.org/10.1063/5.0125432.
Abstract
The generalized Langevin equation (GLE) formalism is a useful theoretical fundament for analyzing dynamical phenomena rigorously. Despite the systematic formulation of dynamics theories with practical approximations, however, the applicability of GLE-based methods is still limited to simple polyatomic liquids due to the approximate treatment of molecular orientations involved in the static molecular liquid theory. Here, we propose an exact framework of dynamics based on the GLE formalism incorporating the energy representation theory of solution, an alternative static molecular liquid theory. A fundamental idea is the projection of the relative positions and orientations of solvents around a solute onto the solute-solvent interaction, namely the energy coordinate, enabling us to describe the dynamics on a one-dimensional coordinate. Introducing systematic approximations, such as the overdamped limit, leads to the molecular diffusion equation in the energy representation that is described in terms of the distribution function of solvents on the energy coordinate and the diffusion coefficients. The present theory is applied to the solvation dynamics triggered by the photoexcitation of benzonitrile. The long-time behavior of the solvation time correlation function is in good agreement with that obtained by the molecular dynamics simulation.
Publisher
American Institute of Physics Inc.
Source Title
Journal of Chemical Physics
Volume (Issue)
157(24)
Page
244505
Date of Issued
2022-12-28
Language
English
Handle URL
https://hdl.handle.net/11094/97734
PISSN
00219606
eISSN
10897690
Relation.isIdenticalTo
DOI (Publisher Version)
https://doi.org/10.1063/5.0125432
Access Rights
open access
CopyRight
This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Okita K., Kasahara K., Matubayasi N.. Diffusion theory of molecular liquids in the energy representation and application to solvation dynamics. Journal of Chemical Physics 157, 244505 (2022) and may be found at https://doi.org/10.1063/5.0125432.
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Version of Record
Category
学術雑誌論文 Journal Article