| Autor: |
Damour Y; Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, 31062 Toulouse, France., Quintero-Monsebaiz R; Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, 31062 Toulouse, France., Caffarel M; Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, 31062 Toulouse, France., Jacquemin D; Nantes Université, CNRS, CEISAM UMR 6230, F-44000 Nantes, France.; Institut Universitaire de France (IUF), F-75005 Paris, France., Kossoski F; Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, 31062 Toulouse, France., Scemama A; Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, 31062 Toulouse, France., Loos PF; Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, 31062 Toulouse, France. |
| Abstrakt: |
We report ground- and excited-state dipole moments and oscillator strengths (computed in different "gauges" or representations) of full configuration interaction (FCI) quality using the selected configuration interaction method known as Configuration Interaction using a Perturbative Selection made Iteratively (CIPSI). Thanks to a set encompassing 35 ground- and excited-state properties computed in 11 small molecules, the present near-FCI estimates allow us to assess the accuracy of high-order coupled-cluster (CC) calculations including up to quadruple excitations. In particular, we show that incrementing the excitation degree of the CC expansion (from CC with singles and doubles (CCSD) to CC with singles, doubles, and triples (CCSDT) or from CCSDT to CC with singles, doubles, triples, and quadruples (CCSDTQ)) reduces the average error with respect to the near-FCI reference values by approximately 1 order of magnitude. |
