Thermodynamics of ionic solvation: Monte Carlo simulations of aqueous chloride and bromide ions

Journal Article · Thu Dec 04 00:00:00 EST 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100283a017· OSTI ID:6953232

Brooks, III, C L

The methods of thermodynamic perturbation theory have been used to calculate the relative thermodynamic properties for the hydration of chloride and bromide ions in dilute solution. The direct evaluation of derivatives of the partition function is carried out to compute the relative energy and entropy of hydration from a single simulation. The results from this method are of greater precision than those computed from differences involving independent simulations. Thus, a potential computational savings of one-half may be obtained by use of the finite difference formula developed within. The influence of interaction truncation on the relative thermodynamic properties is also discussed. Substantial errors of 10-25% in the relative free energy of hydration may be attributed to truncation effects. A simple model for ion-water energetics and structure is used to analyze the origin of this truncation effect and it is shown that differences in the phase and/or amplitude of the ion-water distribution functions are responsible for the majority of the influence.

• Research Organization: Carnegie-Mellon Univ., Pittsburgh, PA
• OSTI ID: 6953232
• Journal Information: J. Phys. Chem.; (United States), Vol. 90:25
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BROMIDES
THERMODYNAMIC PROPERTIES
CHLORIDES
AQUEOUS SOLUTIONS
MONTE CARLO METHOD
PERTURBATION THEORY
SOLVATION
THEORETICAL DATA
THERMODYNAMICS
BROMINE COMPOUNDS
CHLORINE COMPOUNDS
DATA
DISPERSIONS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
MIXTURES
NUMERICAL DATA
PHYSICAL PROPERTIES
SOLUTIONS
400201* - Chemical & Physicochemical Properties