分子单电子脱附态物理性质的中间态表示方法。II. 基准测试。

Intermediate state representation approach to physical properties of molecular electron-detached states. II. Benchmarking.

机构信息

Interdisciplinary Center for Scientific Computing, Heidelberg University, Im Neuenheimer Feld 205, D-69120 Heidelberg, Germany.

Department of Chemistry, Norwegian University of Science and Technology, 7491 Trondheim, Norway.

出版信息

J Chem Phys. 2020 Jan 14;152(2):024125. doi: 10.1063/1.5137794.

DOI:10.1063/1.5137794

PMID:31941293

Abstract

The third-order algebraic-diagrammatic construction method for studies of electron detachment processes within the electron propagator framework [IP-ADC(3)] was extended to treat the properties of molecular states with a detached electron using the intermediate state representation (ISR) formalism. The second-order ISR(2) equations for the one-particle (transition) density matrix have been derived and implemented as an extension of the IP-(U)ADC(3) method available in the Q-CHEM program. As a first systematic test of the present IP-(U)ADC(3)/ISR(2) method, the dipole moments of various electronic states of closed- and open-shell molecules have been computed and compared to full configuration interaction (FCI) results. The present study employing FCI benchmarks also provides the first rigorous estimates for the accuracy of electron detachment energies obtained using the IP-ADC(3) method.

摘要

三阶代数图表构造方法（[IP-ADC(3)]）用于研究电子传播子框架内的电子脱离过程，通过中间态表示（ISR）形式，该方法已被扩展到使用电子脱离的分子态性质。一阶单粒子（跃迁）密度矩阵的二阶 ISR(2)方程已被推导出，并作为 Q-CHEM 程序中可用的 IP-(U)ADC(3)方法的扩展而实现。作为对本 IP-(U)ADC(3)/ISR(2)方法的首次系统测试，已计算了各种闭壳层和开壳层分子的各种电子态的偶极矩，并与完全组态相互作用（FCI）结果进行了比较。本研究采用 FCI 基准，还首次对使用 IP-ADC(3)方法获得的电子脱离能的准确性进行了严格估计。