MOLECULAR-BASIS FOR THE BORN MODEL OF ION SOLVATION

被引:240
作者
ROUX, B [1 ]
YU, HA [1 ]
KARPLUS, M [1 ]
机构
[1] HARVARD UNIV,DEPT CHEM,12 OXFORD ST,CAMBRIDGE,MA 02138
关键词
D O I
10.1021/j100374a057
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Statistical mechanical theory of aqueous solutions is used to provide an interpretation for the Born model of ion hydration at the molecular level. The analysis is based on an asymptotic solution to the extended RISM integral equation in the limit of a large spherical solute. It is shown that a construction of the appropriate direct correlation function yields the Born model for the electrostatic free energy of solvation. In this approximation the free energy of solvation equals half the average solute-solvent interaction energy. Results of the RISM-HNC calculations for microscopic ions as a function of charge are presented, and the Born radius of hydration is interpreted in terms of the first peak in the solute-solvent radial distribution function: in water this leads to different radii for positive and negative ions. Analysis indicates that the Born model gives the dominant contribution to the free energy of charging a microscopic ion in water but that it is not appropriate for the calculation of solvation enthalpies because of their sensitivity to the temperature dependence of the Born radius. © 1990 American Chemical Society.
引用
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页码:4683 / 4688
页数:6
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共 39 条
  • [11] EDSALL JT, 1983, ADV BIOPHYS, V16, P53
  • [12] FRIEDMAN HL, 1973, WATER COMPREHENSIVE, V3, P1
  • [13] SOLVATION ENERGY OF IONS IN DIPOLAR SOLVENTS
    GARISTO, F
    KUSALIK, PG
    PATEY, GN
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1983, 79 (12) : 6294 - 6300
  • [14] CALCULATION OF THE TOTAL ELECTROSTATIC ENERGY OF A MACROMOLECULAR SYSTEM - SOLVATION ENERGIES, BINDING-ENERGIES, AND CONFORMATIONAL-ANALYSIS
    GILSON, MK
    HONIG, B
    [J]. PROTEINS-STRUCTURE FUNCTION AND GENETICS, 1988, 4 (01): : 7 - 18
  • [15] AN EXTENDED RISM EQUATION FOR MOLECULAR POLAR FLUIDS
    HIRATA, F
    ROSSKY, PJ
    [J]. CHEMICAL PHYSICS LETTERS, 1981, 83 (02) : 329 - 334
  • [16] THE INTERIONIC POTENTIAL OF MEAN FORCE IN A MOLECULAR POLAR-SOLVENT FROM AN EXTENDED RISM EQUATION
    HIRATA, F
    ROSSKY, PJ
    PETTITT, BM
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1983, 78 (06) : 4133 - 4144
  • [17] HIRATA F, 1988, INT J QUANTUM CHEM, V15, P179
  • [18] SCREENED POTENTIALS OF THE SITE SITE ION MOLECULAR-MODEL - THE MEAN SPHERICAL APPROXIMATION
    HOLOVKO, MF
    KALYUZHNIJ, YV
    [J]. MOLECULAR PHYSICS, 1989, 66 (02) : 375 - 396
  • [19] FREE-ENERGY CALCULATIONS OF ION HYDRATION - AN ANALYSIS OF THE BORN MODEL IN TERMS OF MICROSCOPIC SIMULATIONS
    JAYARAM, B
    FINE, R
    SHARP, K
    HONIG, B
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (10) : 4320 - 4327
  • [20] COMPARISON OF SIMPLE POTENTIAL FUNCTIONS FOR SIMULATING LIQUID WATER
    JORGENSEN, WL
    CHANDRASEKHAR, J
    MADURA, JD
    IMPEY, RW
    KLEIN, ML
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1983, 79 (02) : 926 - 935