Evaluation of the performances of different atomic charge and nonelectrostatic models in the finite‐difference Poisson–Boltzmann approach
Evaluation of the performances of different atomic charge and nonelectrostatic models in the finite‐difference
Poisson–Boltzmann
approach
复制标题
有限差分泊松-玻尔兹曼方法中不同原子电荷和非静电模型的性能评估
DOI：
10.1002/qua.26560
复制
发表时间：
2020
影响因子：
2.2
通讯作者：
F. Labat
中科院分区：
文献类型：
--
作者：
Dario Vassetti;F. Labat
在这项工作中，我们用隐式溶剂化模型研究了不同的原子电荷模型和非静电模型对中性分子水合能的影响。溶剂化自由能被分为两个主要部分，第一个是通过有限差分方法求解泊松方程得到的体静电的自洽反应场处理，其中溶质电荷密度用原子电荷近似，第二个对应于溶剂化第一壳层中溶质与溶剂之间的短程相互作用。在Hartree-Fock(HF)和B3LYP水平上考虑了五种不同的原子电荷模型(Mulliken，Hirshfeld，Hirshfeld-I，CM5及其迭代版本CM5-I)，包括三种不同的基组，以及两种非静电模型，包括腔、色散和溶剂结构效应(CDS)模型。在所考虑的三个基组上平均，结合到CDS模型中的赫希菲尔德电荷导致了最低的平均无符号误差(MUE)，相对于实验数据的值为0.92MOL/ 。另一方面，将Cm5电荷结合到CDS模型中，得到的Mue为2.02kcal/ ，突出了为广义Born静电学建立的原始CDS参数到不同的静电学模型的低可转换性。然而，通过减小CM5电荷以更好地与原始的CDS模型相平衡，得到的MUE为0.68千卡/ ，这表明在隐式溶剂化模型中，静电和非静电对溶剂化自由能的贡献之间存在着微妙的平衡。
In this work, we investigate the effects of different atomic charge and nonelectrostatic models on the hydration energies of neutral molecules, using an implicit solvation model. The solvation free energy is divided into two main components, the first resulting from a self‐consistent reaction field treatment of the bulk electrostatics obtained by solving the Poisson equation in a finite‐difference (FD) approach where the solute charge density is approximated by atomic charges, the second corresponding to short‐range interactions between the solute and the solvent in the first solvation shell. Five different atomic charge models (Mulliken, Hirshfeld, Hirshfeld‐I, CM5 and its iterative version, CM5‐I) have been considered, both at the Hartree–Fock (HF) and B3LYP levels, with three different basis sets, alongside two nonelectrostatic models including the cavity, dispersion, and solvent structural effects (CDS) model. Averaging over the three considered basis sets, Hirshfeld charges combined to the CDS model led to the lowest mean unsigned error (MUE), with a value of 0.92 kcal/mol with respect to the experimental data. On the other hand, a MUE of 2.02 kcal/mol was obtained with CM5 charges combined to the CDS model, highlighting the low transferability of the original CDS parameters developed for the generalized Born electrostatics to a different electrostatics model. By scaling down the CM5 charges to better balance with the original CDS model, a MUE of 0.68 kcal/mol was however obtained, outlining the delicate balance existing between the electrostatic and nonelectrostatic contributions to the solvation free energy in implicit solvation models.
DOI：
10.1021/acs.jpca.5b03159
发表时间：
2015-06-04
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
Mei Y;Simmonett AC;Pickard FC 4th;DiStasio RA Jr;Brooks BR;Shao Y
通讯作者：
Shao Y