Preferential solvation in urea solutions at different concentrations: Properties from simulation studies

Hironori Kokubo, Bernard Pettitt

Research output: Contribution to journalArticle

74 Citations (Scopus)

Abstract

We performed molecular dynamics simulations of urea solutions at different concentrations with two urea models (OPLS and KBFF) to examine the structures responsible for the thermodynamic solution properties. Our simulation results showed that hydrogen-bonding properties such as the average number of hydrogen bonds and their lifetime distributions were nearly constant at all concentrations between infinite dilution and the solubility limit. This implies that the characterization of urea-water solutions in the molarity concentration scale as nearly ideal is a result of facile local hydrogen bonding rather than a global property. Thus, urea concentration does not influence the local propensity for hydrogen bonds, only how they are satisfied. By comparison, the KBFF model of urea donated fewer hydrogen bonds than OPLS. We found that the KBFF urea model in TIP3P water better reproduced the experimental density and diffusion constant data. Preferential solvation analysis showed that there were weak urea-urea and water-water associations in OPLS solution at short distances, but there were no strong associations. We divided urea molecules into large, medium, and small clusters to examine fluctuation properties and found that any particular urea molecule did not stay in the same cluster for a long time. We found neither persistent nor large clusters.

Original languageEnglish (US)
Pages (from-to)5233-5242
Number of pages10
JournalJournal of Physical Chemistry B
Volume111
Issue number19
DOIs
StatePublished - May 17 2007
Externally publishedYes

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Solvation
ureas
Urea
solvation
Hydrogen bonds
simulation
Water
hydrogen bonds
water
Molecules
hydrogen
guy wires
Dilution
dilution
Molecular dynamics
molecules
solubility
Solubility
Thermodynamics
molecular dynamics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Preferential solvation in urea solutions at different concentrations : Properties from simulation studies. / Kokubo, Hironori; Pettitt, Bernard.

In: Journal of Physical Chemistry B, Vol. 111, No. 19, 17.05.2007, p. 5233-5242.

Research output: Contribution to journalArticle

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