New mean-energy formulae for free energy differences
New mean-energy formulae for free energy differences
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自由能差的新平均能量公式
DOI：
10.1080/00268970500298980
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发表时间：
2005
影响因子：
1.7
通讯作者：
D. Ben‐Amotz
中科院分区：
文献类型：
--
作者：
Fernando O. Raineri *;G. Stell;D. Ben‐Amotz
在经典统计力学的范畴内，我们报告了一些新的精确表达式，用于溶剂化对溶质自由能变化的贡献ΔA，该溶质经历了与溶剂相互作用方式不同的两种状态之间的转换。我们的基本结果是一个耦合参数表达式，它等价于ΔA的通常累积展开式。在我们的公式中，这是来自一个线性耦合参数方案，所有的累积量项以外的第一个收集到一个积分的耦合参数。从这个公式中，与微积分的平均值定理的帮助下，我们推导出精确的一个和两个参考点的平均能量表达式的溶剂化自由能的变化，这两个都不限于线性响应政权。单参考点和双参考点公式都是根据耦合参数的一个独特值（分别为和λ *）给出的，该值是先验未知的（除了在线性响应状态下，我们正好找到它）。在双参考点公式的情况下，我们将δ * 与溶质的（δ = 0）→（δ = 1）变换中沿着中间态取样的溶剂化结构的累积变化联系起来。最后，基于这些发展，我们提出了一个分析的线性相互作用能和扩展线性响应半经验计算方法（广泛用于确定配体/受体生物系统的结合常数），努力了解其统计力学基础以及其适用范围。
We report a number of new exact expressions, within the realm of classical statistical mechanics, for the solvation contribution ΔA to the free energy change of a solute that undergoes a transformation between two states that differ in the way they interact with the solvent. Our basic result is a coupling-parameter expression that is equivalent to the usual cumulant expansion of ΔA. In our formula, which is derived from a linear coupling-parameter scheme, all the cumulant terms beyond the first one are collected into an integral over the coupling parameter. From this formula, with the help of the mean-value theorems of calculus, we derive exact one- and two-reference-point mean-energy expressions for the solvation free energy change, neither of which is limited to the linear response regime. Both the one- and the two-reference point formulae are given in terms of one distinguished value of the coupling parameter ( and ξ*, respectively) that is not known a priori (except in the linear response regime where we find it exactly). In the case of the two-reference-point formula, we relate ξ* with the cumulative changes of the solvation structure along the intermediate states sampled in the (ξ = 0) → (ξ = 1) transformation of the solute. Finally, and based on these developments, we present an analysis of the Linear Interaction Energy and of the Extended Linear Response semi-empirical computational methods (widely used for the determination of binding constants of ligand/receptor biological systems) in an effort to understand their statistical mechanical foundations as well as their domain of applicability.
基于蒙特卡罗模拟的 Xa 因子抑制剂活性分析。
DOI：
10.1021/jm030288d
发表时间：
2003
期刊：
Journal of medicinal chemistry.
影响因子：
--
作者：
Ostrovsky,Dennis;Udier-Blagovic,Marina;Jorgensen,WilliamL
通讯作者：
Jorgensen,WilliamL