Computer experiments on aqueous solution. I. Monte Carlo calculation on the hydration of methanol in an infinitely dilute aqueous solution with a new water–methanol pair potential

Monte Carlo calculations have been carried out both for pure water and an infinitely dilute aqueous solution of methanol at 298.15 K and ordinary density by the Metropolis scheme in NVT ensemble. The total number of molecules is 216, one of which is methanol in the case of aqueous solution. For water–water interaction, the MCY (Matsuoka–Clementi–Yoshimine) potential is used, whereas a new pair potential is determined for water–methanol interaction from ab initio LCAO SCF MO calculations for more than 450 different dimeric configurations with a STO‐3G basis set and subsequent multiparameter fitting of MO data thus obtained to an appropriate potential function with a nonlinear optimization method. For the aqueous methanol solution, 4 500 000 configurations have been generated and the final 1 500 000 are used to obtain average quantities for energy and various distribution functions. It is found that, with the introduction of one methanol molecule, the potential energy and structure of water tend to stabiliz...

[1]  W. L. Jorgensen Quantum and statistical mechanical studies of liquids. 3. Deriving intermolecular potential functions for the water dimer from ab initio calculations , 1979 .

[2]  Alfons Geiger,et al.  Molecular dynamics study of the hydration of Lennard‐Jones solutes , 1979 .

[3]  S. Swaminathan,et al.  A heuristic intermolecular potential function for formaldehyde-water based on ab initio molecular orbital calculations , 1977 .

[4]  N. Metropolis,et al.  Equation of State Calculations by Fast Computing Machines , 1953, Resonance.

[5]  D. Ives,et al.  The structural properties of alcohol–water mixtures , 1966 .

[6]  E. Clementi,et al.  Study of the structure of molecular complexes. XIII. Monte Carlo simulation of liquid water with a configuration interaction pair potential , 1976 .

[7]  K. Nakanishi,et al.  A Monte Carlo study on the size dependence in hydrophobic hydration , 1981 .

[8]  G. Alagona,et al.  Abinitio calculations as a source of intermolecular potential functions. Ethanol–water with a minimal basis set , 1981 .

[9]  M. Rao,et al.  On the force bias Monte Carlo simulation of simple liquids , 1979 .

[10]  E. Clementi,et al.  Study of the structure of molecular complexes. IV. The Hartree‐Fock potential for the water dimer and its application to the liquid state , 1973 .

[11]  J. D. Doll,et al.  Brownian dynamics as smart Monte Carlo simulation , 1978 .

[12]  B. Lu,et al.  Excess Thermodynamic Properties of Aqueous Alcohol Solutions. , 1965 .

[13]  Enrico Clementi,et al.  A theoretical study on the water structure for nucleic acids bases and base pairs in solution at T=300 K , 1980 .

[14]  F. Stillinger,et al.  Improved simulation of liquid water by molecular dynamics , 1974 .

[15]  Harold A. Scheraga,et al.  Structure of Water and Hydrophobic Bonding in Proteins. I. A Model for the Thermodynamic Properties of Liquid Water , 1962 .

[16]  J. D. Bene Theoretical Study of Open Chain Dimers and Trimers Containing CH3OH and H2O , 1971 .

[17]  W. S. Benedict,et al.  Rotation‐Vibration Spectra of Deuterated Water Vapor , 1956 .

[18]  O. Matsuoka,et al.  CI study of the water dimer potential surface , 1976 .

[19]  G. Perron,et al.  Microheterogeneity in aqueous-organic solutions: Heat capacities, volumes and expansibilities of some alcohols, aminoalcohol and tertiary amines in water , 1980 .

[20]  Henry S. Frank,et al.  Free Volume and Entropy in Condensed Systems III. Entropy in Binary Liquid Mixtures; Partial Molal Entropy in Dilute Solutions; Structure and Thermodynamics in Aqueous Electrolytes , 1945 .

[21]  R. Lees,et al.  Torsion–Vibration–Rotation Interactions in Methanol. I. Millimeter Wave Spectrum , 1968 .

[22]  Monte Carlo calculations in the isothermal-isobaric ensemble. 1. Liquid water , 1977 .