An implicit solvent model for SCC-DFTB with Charge-Dependent Radii.
An implicit solvent model for SCC-DFTB with Charge-Dependent Radii.
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DOI：
10.1021/ct1001818
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发表时间：
2010-08-10
影响因子：
5.5
通讯作者：
Cui, Qiang
中科院分区：
文献类型：
--
作者：
Hou, Guanhua;Zhu, Xiao;Cui, Qiang
由于需要快速探索涉及高电荷物质的化学反应的势能面，我们开发了一种近似密度泛函理论的隐式溶剂模型SCC-DFTB。溶剂化自由能的计算使用流行的模型，采用泊松-玻尔兹曼静电和非极性贡献的表面积项。为了平衡具有不同电荷分布的物质的处理，我们使定义介电边界和溶质腔的原子半径取决于溶质电荷分布。具体来说，假设原子半径与Mulliken电荷线性相关，并与溶质电子结构自一致地求解。基准计算表明，该模型的溶剂化自由能的精度与SM6模型相当（特别是对于离子），后者需要更昂贵的DFT计算。基于SCC-DFTB的溶剂化模型具有解析一阶导数和良好的计算速度，可以有效地与高阶QM计算相结合，探索溶液反应的机理。通过对单甲基单磷酸酯（MMP）和三甲基单磷酸酯（TMP）水解的简要分析说明了这一点。还简要讨论了未来可能的改进。
Motivated by the need of rapidly exploring the potential energy surface of chemical reactions that involve highly charged species, we have developed an implicit solvent model for the approximate density functional theory, SCC-DFTB. The solvation free energy is calculated using the popular model that employs Poisson-Boltzmann for electrostatics and a surface-area term for non-polar contributions. To balance the treatment of species with different charge distributions, we make the atomic radii that define the dielectric boundary and solute cavity depend on the solute charge distribution. Specifically, the atomic radii are assumed to be linearly dependent on the Mulliken charges and solved self-consistently together with the solute electronic structure. Benchmark calculations indicate that the model leads to solvation free energies of comparable accuracy to the SM6 model (especially for ions), which requires much more expensive DFT calculations. With analytical first derivatives and favorable computational speed, the SCC-DFTB based solvation model can be effectively used, in conjunction with high-level QM calculations, to explore the mechanism of solution reactions. This is illustrated with a brief analysis of the hydrolysis of mono-methyl mono-phosphate ester (MMP) and tri-methyl mono-phosphate ester (TMP). Possible future improvements are also briefly discussed.
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DOI：
10.1039/ft9949001709
发表时间：
1994-06-21
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS
影响因子：
--
作者：
BARNES, JA;WILKIE, J;WILLIAMS, IH
通讯作者：
WILLIAMS, IH
影响因子：
4.4
作者：
Cui, Q
通讯作者：
Cui, Q
影响因子：
2.3
作者：
AGUILAR, MA;DELVALLE, FJO
通讯作者：
DELVALLE, FJO
DOI：
10.1039/jr9610002670
发表时间：
1961-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY
影响因子：
--
作者：
BARNARD, PW;VERNON, CA;BUNTON, CA
通讯作者：
BUNTON, CA
影响因子：
3
作者：
BROOKS, BR;BRUCCOLERI, RE;KARPLUS, M
通讯作者：
KARPLUS, M