Generalizing Continuum Solvation in Crystal to Nonaqueous Solvents: Implementation, Parametrization, and Application to Molecules and Surfaces,Journal of Chemical Theory and Computation

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Generalizing Continuum Solvation in Crystal to Nonaqueous Solvents: Implementation, Parametrization, and Application to Molecules and Surfaces
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2021-09-06 , DOI: 10.1021/acs.jctc.1c00611
Dario Vassetti ₁ , Ismail Can Oǧuz ₁ , Frédéric Labat ₁

Affiliation

We present an extension of a generalized finite-difference Poisson–Boltzmann (FDPB) continuum solvation model based on a self-consistent reaction field treatment to nonaqueous solvents. Implementation and reparametrization of the cavitation, dispersion, and structural (CDS) effects nonelectrostatic model are presented in CRYSTAL, with applications to both finite and infinite periodic systems. For neutral finite systems, computed errors with respect to available experimental data on free energies of solvation of 2523 solutes in 91 solvents, as well as 144 transfer energies from water to 14 organic solvents are on par with the reference SM12 solvation model for which the CDS parameters have been developed. Calculations performed on a TiO₂ anatase surface and compared to VASPsol data revealed an overall very good agreement of computed solvation energies, surface energies, as well as band structure changes upon solvation in three different solvents, validating the general applicability of the reparametrized FDPB approach to neutral nonperiodic and periodic solutes in aqueous and nonaqueous solvents. For ionic species, while the reparametrized CDS model led to large errors on free energies of solvation of anions, addition of a corrective term based on Abraham’s acidity of the solvent significantly improved the accuracy of the proposed continuum solvation model, leading to errors on aqueous pK_a of a test set of 83 solutes divided by a factor of 4 compared to the reference solvation model based on density (SMD). Overall, therefore, these encouraging results demonstrate that the generalized FDPB continuum solvation model can be applied to a broad range of solutes in various solvents, ranging from finite neutral or charged solutes to extended periodic surfaces.

中文翻译：

将晶体中的连续溶剂化推广到非水溶剂：分子和表面的实现、参数化和应用

我们提出了基于对非水溶剂的自洽反应场处理的广义有限差分泊松-玻尔兹曼 (FDPB) 连续溶剂化模型的扩展。CRYSTAL中介绍了空化、色散和结构 (CDS) 效应非静电模型的实现和重新参数化，可应用于有限和无限周期系统。对于中性有限系统，关于 2523 种溶质在 91 种溶剂中的溶剂化自由能以及从水到 14 种有机溶剂的 144 种转移能的可用实验数据的计算误差与 CDS 的参考 SM12 溶剂化模型相同参数已开发。对 TiO ₂进行的计算锐钛矿表面并与 VASPsol 数据相比，显示计算的溶剂化能、表面能以及在三种不同溶剂中溶剂化时的能带结构变化总体上非常一致，验证了重新参数化 FDPB 方法对中性非周期性和周期性溶质的普遍适用性水性和非水性溶剂。对于离子种类，虽然重新参数化的 CDS 模型导致阴离子溶剂化自由能的较大误差，但添加基于亚伯拉罕的溶剂酸度的校正项显着提高了所提出的连续溶剂化模型的准确性，从而导致水相的误差ķ_一与基于密度 (SMD) 的参考溶剂化模型相比，83 个溶质的测试集除以 4 倍。因此，总的来说，这些令人鼓舞的结果表明，广义 FDPB 连续溶剂化模型可以应用于各种溶剂中的广泛溶质，从有限的中性或带电溶质到扩展的周期性表面。

更新日期：2021-10-12

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