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Coupled cluster theory in the condensed phase within the singles‐T density scheme for the environment response
Wiley Interdisciplinary Reviews: Computational Molecular Science ( IF 11.4 ) Pub Date : 2020-01-22 , DOI: 10.1002/wcms.1463
Marco Caricato 1
Affiliation  

Reliable simulations of molecules in condensed phase require the combination of an accurate quantum mechanical method for the core region, and a realistic model to describe the interaction with the environment. Additionally, this combination should not significantly increase the computational cost of the calculation compared to the corresponding in vacuo case. In this review, we describe the combination of methods based on coupled cluster (CC) theory with polarizable classical models for the environment. We use the polarizable continuum model (PCM) of solvation to discuss the equations, but we also show how the same theoretical framework can be extended to polarizable force fields. The theory is developed within the perturbation theory energy and singles‐T density (PTES) scheme, where the environmental response is computed with the CC single excitation amplitudes as an approximation for the full one‐particle reduced density. The CC‐PTES combination provides the best compromise between accuracy and computational effort for CC calculations in condensed phase, because it includes the response of the environment to the correlation density at the same computational cost of in vacuo CC. We discuss a number of numerical applications for ground and excited state properties, based on the implementation of CC‐PTES with single and double excitations (CCSD‐PTES), which show the reliability and computational efficiency of the method in reproducing experimental or full‐CC data.

中文翻译:

Singles-T密度方案中凝聚相耦合凝聚理论在环境响应中的应用

可靠的凝聚态分子模拟要求结合用于核区的精确量子力学方法和描述与环境相互作用的逼真的模型。另外,与相应的真空情况相比,这种组合不应显着增加计算的计算成本。在这篇综述中,我们描述了基于耦合簇(CC)理论的方法与可极化的经典环境模型的组合。我们使用溶剂化的可极化连续体模型(PCM)来讨论方程,但是我们也展示了如何将相同的理论框架扩展到可极化力场。该理论是在扰动理论能量和单T密度(PTES)方案的基础上发展起来的,其中,环境响应是使用CC单个激发幅度作为完整的单颗粒降低密度的近似值来计算的。CC-PTES组合为冷凝阶段的CC计算提供了准确度和计算工作之间的最佳折衷,因为它以真空CC的相同计算成本包括环境对相关密度的响应。我们基于单激励和双激励的CC-PTES(CCSD-PTES)的实现,讨论了许多基态和激发态特性的数值应用,这些方法证明了该方法在再现实验或全CC时的可靠性和计算效率数据。CC-PTES组合为冷凝阶段的CC计算提供了准确度和计算工作之间的最佳折衷,因为它以真空CC的相同计算成本包括环境对相关密度的响应。我们基于单激励和双激励的CC-PTES(CCSD-PTES)的实现,讨论了许多基态和激发态特性的数值应用,这些方法证明了该方法在再现实验或全CC时的可靠性和计算效率数据。CC-PTES组合为冷凝阶段的CC计算提供了准确度和计算工作之间的最佳折衷,因为它以真空CC的相同计算成本包括环境对相关密度的响应。我们基于单激励和双激励的CC-PTES(CCSD-PTES)的实现,讨论了许多基态和激发态特性的数值应用,这些方法证明了该方法在再现实验或全CC时的可靠性和计算效率数据。
更新日期:2020-01-22
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