AB INITIO CALCULATION OF SOLVATION ENERGIES

我们开发了一种算法来进行量子化学 在电介质中的计算。 我们的电子结构计划 PSGVB首先使用ESP计算静电点电荷 拟合方法 这些费用然后被传递到德尔菲， 通过求解Poisson-Boltzmann方程确定反应场 方程 反应场被表示为 介电边界 这些被传递到PSGVB，PSGVB现在解决了 点电荷场的量子化学方程。 这 迭代过程，直到达到自一致性。 我们已经表明 如果使用精确的气相量子化学方法（GVB + 良好的基组是足够的）溶剂化能量精确到 对于29个分子的测试集，可以计算出~0.6kcal/mole。 最近 工作包括开发一种分析梯度方法， 一种新的有限元Poisson-Boltzmann解法及其改进 通过包含校正的连续介质方法的准确性 短程氢键术语。

Wehavedevelopedanalgorithmforcarryingoutquantumchemical calculations in a dielectric medium. Our electronic structure program PSGVB first calculates electrostatic point charges using an ESP fitting method. These charges are then passed to DELPHI which determines the reaction filed by solving the Poisson-Boltzmann equation. The reaction field is represented as point charges on the dielectric boundary. These are passed to PSGVB which now solves quantum chemical equations in the field of the point charges. This process is iterated until self-consistency is reached. We have shown that if one uses accurate gas phase quantum chemical methods (GVB plus a good basis set is sufficient) solvation energies accurate to ~0.6kcal/mole can be computed for a test set of 29 molecules. Recent work includes development of an analytical gradient method using a novel finite element Poisson-Boltzmann solver and improvement of the accuracy of the continuum method via inclusion of corrections for short-range hydrogen bonding terms.