A molecular Debye-Huckel theory of solvation in polar fluids: An extension of the Born model

作者：Xiao, Tiejun^*; Song, Xueyu

来源：Journal of Chemical Physics, 2017, 147(21): 214502.

DOI：10.1063/1.4998255

• MEAN SPHERICAL MODEL
• LONGITUDINAL DIELECTRIC FUNCTION
• PAIR CORRELATION-FUNCTIONS
• CHARGED HARD-SPHERES
• GAUSSIAN FIELD MODEL
• ION-DIPOLE MIXTURES
• ELECTROLYTE-SOLUTIONS
• INTEGRAL-EQUATION
• THERMODYNAMIC PROPERTIES
• PROTEIN CRYSTALLIZATION

A dielectric response theory of solvation beyond the conventional Born model for polar fluids is presented. The dielectric response of a polar fluid is described by a Born response mode and a linear combination of Debye-Huckel-like response modes that capture the nonlocal response of polar fluids. The Born mode is characterized by a bulk dielectric constant, while a Debye-Huckel mode is characterized by its corresponding Debye screening length. Both the bulk dielectric constant and the Debye screening lengths are determined from the bulk dielectric function of the polar fluid. The linear combination coefficients of the response modes are evaluated in a self-consistent way and can be used to evaluate the electrostatic contribution to the thermodynamic properties of a polar fluid. Our theory is applied to a dipolar hard sphere fluid as well as interaction site models of polar fluids such as water, where the electrostatic contribution to their thermodynamic properties can be obtained accurately. Published by AIP Publishing.

• 出版日期2017-12-7