Multireference Perturbation Theory Combined with PCM and RISM Solvation Models: A Benchmark Study for Chemical Energetics
Multireference Perturbation Theory Combined with PCM and RISM Solvation Models: A Benchmark Study for Chemical Energetics
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多参考扰动理论与 PCM 和 RISM 溶剂化模型相结合：化学能量学的基准研究
DOI：
10.1021/acs.jpca.1c05944
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Yanai Takeshi
中科院分区：
文献类型：
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作者：
Saitow Masaaki;Hori Keisuke;Yoshikawa Ayaka;Shimizu Ryosuke Y.;Yokogawa Daisuke;Yanai Takeshi
可极化连续介质模型（PCM）是量子化学计算中考虑溶剂化效应的最广泛使用的方法之一。在本文中，我们进行了一系列基准计算，以评估极性溶剂中分子系统的 PCM 方案与二阶完整活性空间微扰理论 (CASPT2) 相结合的准确性。对于具有广泛共轭 π 轨道的溶质分子（以细长共轭芳基碳烯为例），我们将 ab 初始密度矩阵重正化群算法纳入 PCM-CASPT2 方法。在之前的工作中，我们提出了将 DMRG-CASPT2 方法与参考相互作用位点模型 (RISM) 理论相结合，使用径向分布函数来描述溶剂化效应，并将其性能与广泛使用的密度泛函方法 (PCM-TD-DFT) 进行比较。这里的工作使我们能够进一步展示对 RISM 模型与具有相同水平的波函数处理（(DMRG-)CASPT2 理论）的 PCM 的更全面的评估，以实现溶剂化化学系统的高精度电子结构计算。除了 PCM 模型无法正确描述氢键外，PCM-CASPT2 模型的准确性在大多数情况下与 RISM 模型相当。
The polarizable continuum model (PCM) has been one of the most widely used approaches to take into account the solvation effect in quantum chemical calculations. In this paper, we performed a series of benchmark calculations to assess the accuracy of the PCM scheme combined with the second-order complete-active-space perturbation theory (CASPT2) for molecular systems in polar solvents. For solute molecules with extensive conjugated π orbitals, exemplified by elongated conjugated arylcarbenes, we have incorporated theab initiodensity matrix renormalization group algorithm into the PCM-CASPT2 method. In the previous work, we presented a combination of the DMRG-CASPT2 method with the reference interaction site model (RISM) theory for describing the solvation effect using the radial distribution function and compared its performance to the widely used density-functional approaches (PCM-TD-DFT). The work here allows us to further show a more thorough assessment of the RISM model compared to the PCM with an equal level of the wave function treatment, the (DMRG-)CASPT2 theory, toward a high-accuracy electronic structure calculations for solvated chemical systems. With the exception that the PCM models are not capable of properly describing the hydrogen bondings, accuracy of the PCM-CASPT2 model is in most cases quite comparable to the RISM counterpart.