Multireference Correlated Oscillator Strengths from Adiabatic Connection Approaches Based on Extended Random Phase Approximation

基于扩展随机相位近似的绝热连接方法的多参考相关振荡器强度

阅读:1

Abstract

We show that accurate oscillator strengths can be obtained from adiabatic connection (AC) approaches based on the extended random phase approximation (ERPA) combined with multireference (complete active space, CAS) wave functions. The oscillator strengths calculated using the perturbation-corrected ERPA transition density matrices, proposed in this work, and the excitation energies calculated with recently introduced AC correlation energy methods, AC0 and AC0D, compete with accuracy in the perturbational CASPT2 approach and require less computational effort. AC0 and AC0D methods scale more favorably with the number of active orbitals than multiconfigurational perturbation approaches like CASPT2 and NEVPT2 thanks to their dependence on reduced density matrices up to the order of 2. Importantly, the newly developed approach for computing correlated transition dipole moments does not entail any additional costs, as all intermediate quantities become available when AC0 energies are being computed. We also test the performance of the recently proposed AC method corrected for the negative-transition contributions to the correlation energy, AC0D, for triplet excitation energies. Similarly, as for the singlet excitations, the correction improves the performance of the AC0 method, particularly for the low-lying excited states.

特别声明

1、本页面内容包含部分的内容是基于公开信息的合理引用;引用内容仅为补充信息,不代表本站立场。

2、若认为本页面引用内容涉及侵权,请及时与本站联系,我们将第一时间处理。

3、其他媒体/个人如需使用本页面原创内容,需注明“来源:[生知库]”并获得授权;使用引用内容的,需自行联系原作者获得许可。

4、投稿及合作请联系:info@biocloudy.com。