Goletto Linda, Gómez Sara, Andersen Josefine H, Koch Henrik, Giovannini Tommaso
Department of Chemistry, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway.
Scuola Normale Superiore, Piazza dei Cavalieri 7, IT-56126 Pisa, PI, Italy.
Phys Chem Chem Phys. 2022 Nov 23;24(45):27866-27878. doi: 10.1039/d2cp04512e.
We present a computational study of static and dynamic linear polarizabilities in solution. We use different theoretical approaches to describe solvent effects, ranging from quantum mechanics/molecular mechanics (QM/MM) to quantum embedding approaches. In particular, we consider non-polarizable and polarizable QM/MM methods, the latter based on the fluctuating charge (FQ) force field. In addition, we use a quantum embedding method defined in the context of multilevel Hartree-Fock (MLHF), where the system is divided into active and inactive regions, and combine it with a third layer described by means of the FQ model. The multiscale approaches are then used as reference wave functions for equation-of-motion coupled cluster (EOM-CC) response properties, allowing for the account of electron correlation. The developed models are applied to the calculation of linear response properties of two organic moieties-namely, -nitroaniline and benzonitrile-in non-aqueous solvents-1,4-dioxane, acetonitrile, and tetrahydrofuran. The computed polarizabilities are then discussed in terms of the physico-chemical solute-solvent interactions described by each method (electrostatic, polarization and Pauli repulsion), and finally compared with the available experimental references.
我们展示了溶液中静态和动态线性极化率的计算研究。我们使用不同的理论方法来描述溶剂效应，范围从量子力学/分子力学（QM/MM）到量子嵌入方法。特别地，我们考虑了不可极化和可极化的QM/MM方法，后者基于波动电荷（FQ）力场。此外，我们使用了在多级Hartree-Fock（MLHF）背景下定义的量子嵌入方法，其中系统被划分为活性区域和非活性区域，并将其与通过FQ模型描述的第三层相结合。然后，多尺度方法被用作运动方程耦合簇（EOM-CC）响应性质的参考波函数，以考虑电子相关性。所开发的模型被应用于计算两种有机部分——即对硝基苯胺和苯甲腈——在非水溶剂1,4-二氧六环、乙腈和四氢呋喃中的线性响应性质。然后根据每种方法所描述的物理化学溶质-溶剂相互作用（静电、极化和泡利排斥）对计算得到的极化率进行讨论，最后与现有的实验参考文献进行比较。
