Benchmarking the conductor-like polarizable continuum model (CPCM) for aqueous solvation free energies of neutral and ionic organic molecules
Benchmarking the conductor-like polarizable continuum model (CPCM) for aqueous solvation free energies of neutral and ionic organic molecules
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DOI：
10.1021/ct049977a
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发表时间：
2005-01-01
影响因子：
5.5
通讯作者：
Houk, KN
中科院分区：
文献类型：
--
作者：
Takano, Y;Houk, KN
导体样极化连续模型（CPCM）使用几个空腔模型被施加到计算水溶剂化自由能的一些有机分子（30个中性分子，21个阴离子，和19个阳离子）。从空腔模型、计算方法、计算时间和水溶液pK（a）值的角度，将计算的溶剂化自由能与可用的实验数据进行比较。HF/6-31+G（d）//HF/6-31+G（d）和HF/6-31+G（d）//B3 LYP/6-31+G（d）具有UAKS腔，其中半径用PBE 0/6-31 G（d）优化，提供与现有实验数据最一致的水溶剂化效应。与实验值的平均绝对偏差为2.6kcal/mol。对乙酸甲酯在水中的碱催化水解反应进行了MP2/6-31++G（d，p）//HF/6 -31 +G（d）和CPCM-UAKS（HF/6-31 +G（d））计算。
The conductor-like polarizable continuum model (CPCM) using several cavity models is applied to compute aqueous solvation free energies for a number of organic molecules (30 neutral molecules, 21 anions, and 19 cations). The calculated solvation free energies are compared to the available experimental data from the viewpoint of cavity models, computational methods, calculation time, and aqueous pK(a) values. The HF/6-31+G(d)//HF/6-31+G(d) and the HF/6-31+G(d)//B3LYP/6-31+G(d) with the UAKS cavities, in which radii are optimized with PBE0/6-31 G(d), provide aqueous solvation effects in best agreement with available experimental data. The mean absolute deviations from experiment are 2.6 kcal/mol. The MP2/6-31++G(d,p)//HF/6-31 +G(d) with the CPCM-UAKS(HF/6-31 +G(d)) calculation is also performed for the base-catalyzed hydrolysis of methyl acetate in water.