Department of Chemical and Biological Engineering, SUNY at Buffalo, Buffalo, New York 14260, USA.
J Chem Phys. 2010 Nov 21;133(19):194105. doi: 10.1063/1.3499318.
A water molecule in the vicinity of a hydrophobic surface forms fewer hydrogen bonds than a bulk molecule because the surface restricts the space available for other water molecules necessary for its hydrogen-bonding. In this vicinity, the number of hydrogen bonds per water molecule depends on its distance to the surface. Considering the number of hydrogen bonds per bulk water molecule (available experimentally) as the only reference quantity, we propose an improved probabilistic approach to water hydrogen-bonding that allows one to obtain an analytic expression for this dependence. (The original version of this approach [Y. S. Djikaev and E. Ruckenstein, J. Chem. Phys. 130, 124713 (2009)] provides the number of hydrogen bonds per water molecule in the vicinity of a hydrophobic surface as an average over all possible locations and orientations of the molecule.) This function (the number of hydrogen bonds per water molecule versus its distance to a hydrophobic surface) can be used to develop analytic models for the effect of hydrogen-bonding on the hydration of hydrophobic particles and their solvent-mediated interaction. Presenting a model for the latter, we also examine the temperature effect on the solvent-mediated interaction of two parallel hydrophobic plates.
在疏水表面附近，一个水分子形成的氢键比体相分子少，因为表面限制了其他水分子形成氢键所需的空间。在这个附近，每个水分子的氢键数取决于它与表面的距离。考虑到体相水分子的氢键数（可通过实验获得）作为唯一的参考量，我们提出了一种改进的水氢键概率方法，该方法可以得到这种依赖性的解析表达式。（该方法的原始版本[Y. S. Djikaev 和 E. Ruckenstein，J. Chem. Phys. 130, 124713 (2009)]将疏水表面附近每个水分子的氢键数作为分子所有可能位置和取向的平均值。）这个函数（每个水分子的氢键数与其到疏水表面的距离的关系）可以用于开发氢键对疏水粒子水合作用及其溶剂介导相互作用的影响的分析模型。本文提出了后者的模型，还研究了温度对两个平行疏水板之间溶剂介导相互作用的影响。
