Wilson WD, Schaldach CM
Sandia National Laboratories, Livermore, California, 94550
J Colloid Interface Sci. 1998 Dec 15;208(2):546-554. doi: 10.1006/jcis.1998.5815.
We present a method for the calculation of the binding and rotational energies of neutral (H2S) and charged (HS-) molecules impinging upon a charged and polarizable (Cu <100>) surface in the presence of an electrolyte. A molecular surface is constructed surrounding the H2S and HS- molecules forming boundary elements. A coupled Schrödinger-Poisson-Boltzmann iterative procedure treats the electronic structure of the molecules at the 6-31G**/MP2 level of theory and includes solvation effects through the single and double layers of charge induced by the electronic distribution. The molecule, together with its charged layers, forms a molecular single and double layer, an object which then interacts with a polarizable Gouy-Chapman plane within the electrolyte. The induced charge at the molecular surface resulting from this external electric field is obtained by solving a second set of boundary element equations. The induced polarization of the solid surface created by the impinging molecular ion is treated by a modified method of images. Repulsive interactions between the atoms of the molecule and those of the surface are obtained using a rigid-ion Hartree-Fock method. Binding energies of the molecule to the surface are determined as a function of the real surface charge imposed and also the ionic strength of the solution. It is found that surface charges can completely (180 degrees) reorient these molecules and that the counterions in the solution can completely screen binding effects of even large surface charges. Solid surface polarization can be significant in low dielectric constant solvents and is also reduced by counterions. Copyright 1998 Academic Press.
我们提出了一种计算在电解质存在下，中性（H₂S）和带电（HS⁻）分子撞击带电且可极化（Cu <100>）表面时的结合能和旋转能的方法。围绕H₂S和HS⁻分子构建分子表面，形成边界元素。一种耦合的薛定谔 - 泊松 - 玻尔兹曼迭代程序在6 - 31G**/MP2理论水平上处理分子的电子结构，并通过由电子分布诱导的单层和双层电荷来包括溶剂化效应。分子及其带电层形成分子单层和双层，该物体随后与电解质内的可极化古依 - 查普曼平面相互作用。通过求解第二组边界元素方程获得由该外部电场在分子表面产生的感应电荷。撞击分子离子在固体表面产生的感应极化通过改进的镜像法处理。使用刚性离子哈特里 - 福克方法获得分子原子与表面原子之间的排斥相互作用。分子与表面的结合能被确定为所施加的实际表面电荷以及溶液离子强度的函数。发现表面电荷可以使这些分子完全重新定向（180度），并且溶液中的抗衡离子可以完全屏蔽甚至大表面电荷的结合效应。在低介电常数溶剂中，固体表面极化可能很显著，并且也会被抗衡离子降低。版权所有1998年学术出版社。
