Suppr超能文献

一种具有电荷依赖半径的SCC-DFTB隐式溶剂模型。

An implicit solvent model for SCC-DFTB with Charge-Dependent Radii.

作者信息

Hou Guanhua, Zhu Xiao, Cui Qiang

机构信息

Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin, Madison, 1101 University Ave, Madison, WI 53706.

出版信息

J Chem Theory Comput. 2010 Aug 10;6(8):2303-2314. doi: 10.1021/ct1001818.

Abstract

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.

摘要

出于快速探索涉及高电荷物种的化学反应势能面的需求,我们为近似密度泛函理论SCC-DFTB开发了一种隐式溶剂模型。使用流行的模型计算溶剂化自由能,该模型采用泊松-玻尔兹曼方程处理静电作用,并使用表面积项处理非极性贡献。为了平衡对具有不同电荷分布的物种的处理,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。具体而言,假设原子半径与穆利肯电荷呈线性相关,并与溶质电子结构一起自洽求解。基准计算表明,该模型得到的溶剂化自由能精度与SM6模型相当(特别是对于离子),而SM6模型需要更昂贵的密度泛函理论计算。由于具有解析一阶导数且计算速度快,基于SCC-DFTB的溶剂化模型可以与高水平量子力学计算相结合,有效地用于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)水解的简要分析进行了说明。还简要讨论了未来可能的改进。

文献AI研究员

20分钟写一篇综述,助力文献阅读效率提升50倍。

立即体验

用中文搜PubMed

大模型驱动的PubMed中文搜索引擎

马上搜索

文档翻译

学术文献翻译模型,支持多种主流文档格式。

立即体验