当前位置: X-MOL 学术J. Chem. Theory Comput. › 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.)
Linear-Response Density Cumulant Theory for Excited Electronic States
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-06-21 00:00:00 , DOI: 10.1021/acs.jctc.8b00326
Andreas V. Copan 1 , Alexander Yu. Sokolov 1
Affiliation  

We present a linear-response formulation of density cumulant theory (DCT) that provides a balanced and accurate description of many electronic states simultaneously. In the original DCT formulation, only information about a single electronic state (usually, the ground state) is obtained. We discuss the derivation of linear-response DCT, present its implementation for the ODC-12 method (LR-ODC-12), and benchmark its performance for excitation energies in small molecules (N2, CO, HCN, HNC, C2H2, and H2CO), as well as challenging excited states in ethylene, butadiene, and hexatriene. For small molecules, LR-ODC-12 shows smaller mean absolute errors in excitation energies than equation-of-motion coupled cluster theory with single and double excitations (EOM-CCSD), relative to the reference data from EOM-CCSDT. In a study of butadiene and hexatriene, LR-ODC-12 correctly describes the relative energies of the singly excited 11Bu and the doubly excited 21Ag states, in excellent agreement with highly accurate semistochastic heat-bath configuration interaction results, while EOM-CCSD overestimates the energy of the 21Ag state by almost 1 eV. Our results demonstrate that linear-response DCT is a promising theoretical approach for excited states of molecules.

中文翻译:

激发电子态的线性响应密度累积理论

我们提出了密度累积量理论(DCT)的线性响应公式,该公式同时提供了许多电子状态的平衡和准确描述。在原始DCT公式中,仅获得有关单个电子状态(通常是基态)的信息。我们讨论了线性响应DCT的推导,介绍了ODC-12方法(LR-ODC-12)的实现,并针对小分子(N 2,CO,HCN,HNC,C 2 H)中激发能的性能进行了基准测试。2和H 2CO),以及在乙烯,丁二烯和己三烯中具有挑战性的激发态。对于小分子,相对于来自EOM-CCSDT的参考数据,LR-ODC-12在运动能量方程式中的单次和双次激发(EOM-CCSD)均显示出较小的激发能量平均绝对误差。在对丁二烯和己三烯的研究中,LR-ODC-12正确地描述了单激发1 1 B u和双激发2 1 A g态的相对能量,与高度精确的半随机热浴结构相互作用结果极佳地吻合,而EOM-CCSD高估了2 1 A g的能量状态几乎提高了1 eV。我们的结果表明,线性响应DCT是分子激发态的有前途的理论方法。
更新日期:2018-06-21
down
wechat
bug