论文标题

溶剂化系统的线性响应特性:一项计算研究

Linear Response Properties of Solvated Systems: A Computational Study

论文作者

Goletto, Linda, Gómez, Sara, Andersen, Josefine H., Koch, Henrik, Giovannini, Tommaso

论文摘要

我们介绍了解决方案中静态和动态线性极化的计算研究。我们使用不同的理论方法来描述溶剂效应,从量子力学/分子力学(QM/mm)到量子嵌入方法。特别是,我们考虑了不可极化且可极化的QM/mm方法,后者基于波动电荷(FQ)力场。此外,我们使用在多级Hartree-fock(MLHF)上下文中定义的量子嵌入方法,该方法将系统分为活动和不活动区域,并将其与通过FQ模型所描述的第三层结合。然后将多尺度方法用作运动方程耦合群集(EOM-CC)响应属性的参考波函数,从而允许电子相关性的描述。开发的模型应用于在非水溶剂中的两个有机部分的线性响应特性(即二硝基苯胺和苯硝基) - 1,4-二氧烷,乙腈和四氢呋喃。然后,根据每种方法(静电,极化和Pauli排斥)描述的物理化学溶质 - 溶剂相互作用来讨论计算的极化能力,并最终与可用的实验参考文献进行了比较。

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, para-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.

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