Towards Near-Exact Solutions of Molecular Electronic Structure: Full Coupled-Cluster Reduction with a Second-Order Perturbative Correction,The Journal of Physical Chemistry Letters

当前位置： X-MOL 学术 › J. Phys. Chem. Lett. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Towards Near-Exact Solutions of Molecular Electronic Structure: Full Coupled-Cluster Reduction with a Second-Order Perturbative Correction
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-11-04 , DOI: 10.1021/acs.jpclett.0c03084
Enhua Xu ₁ , Motoyuki Uejima ₁ , Seiichiro L. Ten-no _{1,

2}

Affiliation

We introduce a new augmented adaptation of the recently developed full coupled-cluster reduction (FCCR) with a second-order perturbative correction, abbreviated as FCCR(2). FCCR is a selected coupled-cluster expansion aimed at optimally reducing the excitation manifold and commutator expansions for high-rank excitations for obtaining accurate solutions of the electronic Schödinger equation in a size-extensive manner. The present FCCR(2) enables estimating the residual correlation of FCCR by the second-order perturbative correction E⁽²⁾ from the complementary space of the FCCR projection manifold. The linear relationship between E⁽²⁾ and the energy of FCCR(2) allows accurate estimates of near-exact energies for a wide variety of molecules with strong electron correlation. The potential of the method is demonstrated using challenging cases, the ground-state electronic energy of the benzene molecule in equilibrium and stretched geometries, and the isomerization energy of the transition metal complex [Cu(NH₃)]₂O₂²⁺.

中文翻译：

迈向分子电子结构的精确解决方案：具有二阶扰动校正的全耦合簇还原

我们引入了对新开发的全耦合聚类约简（FCCR）的新增强适应，并带有二阶扰动校正，缩写为FCCR（2）。FCCR是一种选定的耦合群集扩展，旨在针对高阶励磁最佳地减少励磁歧管和换向器扩展，从而以尺寸扩展的方式获得电子Schödinger方程的精确解。本FCCR（2）使得能够通过FCCR投影歧管的互补空间通过二阶微扰校正E ^（2）来估计FCCR的剩余相关性。E ^（2）之间的线性关系FCCR（2）的能量可以精确估计具有强电子相关性的各种分子的近精确能量。在具有挑战性的情况，平衡和拉伸几何结构中苯分子的基态电子能以及过渡金属配合物[Cu（NH ₃）] ₂ O ₂²⁺的异构化能中证明了该方法的潜力。

更新日期：2020-11-19

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11