Reduced‐scaling coupled cluster response theory: Challenges and opportunities,Wiley Interdisciplinary Reviews: Computational Molecular Science

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Reduced‐scaling coupled cluster response theory: Challenges and opportunities
Wiley Interdisciplinary Reviews: Computational Molecular Science ( IF 16.8 ) Pub Date : 2019-01-08 , DOI: 10.1002/wcms.1406
T. Daniel Crawford _{1,

2} , Ashutosh Kumar ₁ , Alexandre P. Bazanté ₁ , Roberto Di Remigio _{1,

3}

Affiliation

We review the current state of reduced‐scaling electron correlation methods, particularly coupled‐cluster theory for the simulation and prediction of molecular response properties. The successes of local‐coupled‐cluster and related approaches are well known for reaction energies, thermodynamic constants, dipole moments, and so forth—properties that depend primarily on the quality of the ground‐state wave function. However, much more challenging are higher‐order properties such as polarizabilities, hyperpolarizabilities, optical rotations, magnetizabilities, and others that also require accurate representation of the derivative of the wave function to external electromagnetic fields. We discuss a range of methods for improving the correlation domains of such perturbed wave functions, including the use of “perturbation‐aware” natural orbitals that are customized for the property of interest. In addition, we consider the viability and potential of promising, but still‐emerging methods such as stochastic and real‐time coupled‐cluster approaches, for which the localizability of the field‐dependent wave function may be more controllable than for conventional response theory.

中文翻译：

降级耦合聚类响应理论：挑战与机遇

我们回顾了降尺度电子相关方法的现状，特别是耦合聚类理论，用于模拟和预测分子响应特性。局部耦合簇和相关方法的成功在反应能，热力学常数，偶极矩等方面是众所周知的，这些属性主要取决于基态波函数的质量。但是，更具挑战性的是高阶性质，例如极化率，超极化率，旋光性，磁化率，以及其他也需要精确表示导数的性质函数对外部电磁场的影响。我们讨论了用于改善此类扰动波函数的相关域的一系列方法，包括使用针对感兴趣属性定制的“感知扰动”的自然轨道。此外，我们考虑了有前途但仍在不断涌现的方法（例如随机和实时耦合聚类方法）的可行性和潜力，对于这些方法，与传统的响应理论相比，场相关波函数的定位性可能更可控。

更新日期：2019-01-08

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