Enthalpy-entropy contributions to the potential of mean force of nanoscopic hydrophobic solutes

Niharendu Choudhury, Bernard Pettitt

Research output: Contribution to journalArticle

98 Citations (Scopus)

Abstract

Entropic and enthalpic contributions to the hydrophobic interaction between nanoscopic hydrophobic solutes, modeled as graphene plates in water, have been calculated using molecular dynamics simulations in the isothermal-isobaric (NPT) ensemble with free energy perturbation methodology. We find the stabilizing contribution to the free energy of association (contact pair formation) to be the favorable entropic part, the enthalpic contribution being highly unfavorable. The desolvation barrier is dominated by the unfavorable enthalpic contribution, despite a fairly large favorable entropic compensation. The enthalpic contributions, incorporating the Lennard-Jones solute-solvent terms, largely determine the stability of the solvent separated configuration. We decompose the enthalpy into a direct solute-solute term, the solute-solvent interactions, and the remainder that contains pressure-volume work as well as contributions due to solvent reorganization. The enthalpic contribution due to changes in water-water interactions arising from solvent reorganization around the solute molecules is shown to have major contribution in the solvent induced enthalpy change.

Original languageEnglish (US)
Pages (from-to)8459-8463
Number of pages5
JournalJournal of Physical Chemistry B
Volume110
Issue number16
DOIs
StatePublished - Apr 27 2006
Externally publishedYes

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Enthalpy
solutes
Entropy
enthalpy
entropy
Free energy
Water
free energy
water
Graphite
interactions
Graphene
Molecular dynamics
graphene
Association reactions
methodology
molecular dynamics
perturbation
Molecules
Computer simulation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Enthalpy-entropy contributions to the potential of mean force of nanoscopic hydrophobic solutes. / Choudhury, Niharendu; Pettitt, Bernard.

In: Journal of Physical Chemistry B, Vol. 110, No. 16, 27.04.2006, p. 8459-8463.

Research output: Contribution to journalArticle

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