How and why coupled-cluster theory became the pre-eminent method in an ab initio quantum chemistry
How and why coupled-cluster theory became the pre-eminent method in an ab initio quantum chemistry
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DOI：
10.1016/b978-044451719-7/50085-8
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发表时间：
2005-01-01
期刊：
影响因子：
--
通讯作者：
Bartlett, Rodney J.
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文献类型：
--
作者：
Bartlett, Rodney J.
相关问题一直是量子化学的焦点超过40年，涵盖了本卷。今天，耦合簇方法通常为小于或接近20个原子的分子提供最佳的数值解决方案，在严密性和对正确答案的系统收敛性方面。耦合团簇（CC）理论不是变分的，但更重要的是，它是尺寸广泛的，使得能量差异有意义，并可以应用于聚合物和固体等扩展系统。CC比类似的组态相互作用方法更有效地引入了更高的激励，而且成本更低。分析梯度作为一种非变分方法，在CC理论中的应用与其他方法相比，需要有新的发展。这些新的发展强调了CC泛函的作用，它是CC理论在能量、力、密度矩阵以及基态和运动方程（EOM-CC）激发态性质中的基础。后者也允许方便地应用于单，双等电离和电子连接状态。在一个客观的，但个人的，第一手的叙述中，列举了导致耦合簇理论及其在化学中的广泛应用的批判思想的演变。
The correlation problem has been a focal point of quantum chemistry for more than the 40 years covered by this volume. Today, coupled-cluster methods typically offer its best numerical solution for molecules of less than or similar to 20 atoms in terms of rigor and systematic convergence to the right answer. Coupled-cluster (CC) theory is not variational, but, more importantly, it is size-extensive making energy differences meaningful and applications to extended systems like polymers and solids possible. CC introduces higher excitations much more effectively and at less expense than analogous configuration interaction methods. As a non-variational method, analytical gradients in CC theory require new developments compared to other methods. These new developments emphasize the role of the CC functional that underlies the CC theory for energies, forces, density matrices, and properties of ground and equation-of-motion (EOM-CC) excited states. The latter also permits facile applications for single, doubly, etc. ionized and electron-attached states. The evolution of the critical ideas that lead to coupled-cluster theory and its extensive applications in chemistry are enumerated, in an objective, but personal, first-hand account.