Jump to main content
Jump to site search

Issue 47, 2006
Previous Article Next Article

Computational assessment of the entropy of solvation of small-sized hydrophobic entities

Author affiliations

Abstract

A high level polarizable force field is used to study the temperature dependence of hydrophobic hydration of small-sized molecules from computer simulations. Molecular dynamics (MD) simulations of liquid water at various temperatures form the basis of free energy perturbation calculations that consider the onset and growth of a repulsive sphere. This repulsive sphere acts as a model construct for the hydrophobic species. In the present study, an extension is pursued for seven independent target temperatures, ranging from close to the freezing point almost up to the boiling point of liquid water under standard conditions. Care is taken to maintain proper physico-chemical model descriptions by cross-checking with experimental water densities at the selected target temperatures. The polarizable force field description of molecular water turns out to be suitable throughout the entire temperature domain considered. Derivatives of the computed free energies of hydrophobic hydration with respect to the temperature give access to the changes in entropy. In practice the entropy differential is determined from the negative of the slope of tangential lines formed at a certain target temperature in the free energy profile. The obtained changes in entropy are negative for small-sized cavities, and hence reconfirm the basic ideas of the Lum–Chandler–Weeks theory on hydrophobic hydration of small-sized solutes.

Graphical abstract: Computational assessment of the entropy of solvation of small-sized hydrophobic entities

Back to tab navigation

Supplementary files

Publication details

The article was received on 03 Aug 2006, accepted on 16 Oct 2006 and first published on 07 Nov 2006


Article type: Paper
DOI: 10.1039/B611200E
Citation: Phys. Chem. Chem. Phys., 2006,8, 5515-5521
  •   Request permissions

    Computational assessment of the entropy of solvation of small-sized hydrophobic entities

    R. Mahajan, D. Kranzlmüller, J. Volkert, U. H. E. Hansmann and S. Höfinger, Phys. Chem. Chem. Phys., 2006, 8, 5515
    DOI: 10.1039/B611200E

Search articles by author

Spotlight

Advertisements