A solvation-free-energy functional: A reference-modified density functional formulation

Tomonari Sumi, Ayori Mitsutake, Yutaka Maruyama

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The three-dimensional reference interaction site model (3D-RISM) theory, which is one of the most applicable integral equation theories for molecular liquids, overestimates the absolute values of solvation-free-energy (SFE) for large solute molecules in water. To improve the free-energy density functional for the SFE of solute molecules, we propose a reference-modified density functional theory (RMDFT) that is a general theoretical approach to construct the free-energy density functional systematically. In the RMDFT formulation, hard-sphere (HS) fluids are introduced as the reference system instead of an ideal polyatomic molecular gas, which has been regarded as the appropriate reference system of the interaction-site-model density functional theory for polyatomic molecular fluids. We show that using RMDFT with a reference HS system can significantly improve the absolute values of the SFE for a set of neutral amino acid side-chain analogues as well as for 504 small organic molecules.

Original languageEnglish
Pages (from-to)1359-1369
Number of pages11
JournalJournal of Computational Chemistry
Volume36
Issue number18
DOIs
Publication statusPublished - Jul 1 2015

Fingerprint

Solvation
Energy Functional
Density Functional
Free energy
Free Energy
Density functional theory
Formulation
Molecules
Absolute value
Energy Density
Neutral Amino Acids
Fluids
Hard-sphere Fluid
Integral equations
Hard Spheres
Amino acids
Interaction
3D Model
Gases
Amino Acids

Keywords

  • 3D-RISM theory
  • amino acid side-chain
  • chignolin
  • classical density functional theory
  • salvation-free-energy
  • water

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

A solvation-free-energy functional : A reference-modified density functional formulation. / Sumi, Tomonari; Mitsutake, Ayori; Maruyama, Yutaka.

In: Journal of Computational Chemistry, Vol. 36, No. 18, 01.07.2015, p. 1359-1369.

Research output: Contribution to journalArticle

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