Spin-flip equation-of-motion coupled cluster method with singles, doubles and (full) triples: computational implementation and some pilot applications

• Published in: Physical chemistry chemical physics : PCCP Vol. 26; no. 31; pp. 2124 - 21212
• Main Authors: Manisha, Manohar, Prashant Uday
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 07.08.2024
• Subjects: Algorithms; Chemical bonds; Clusters; Configuration interaction; Energy gap; Energy of dissociation; Self consistent fields
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/d4cp02265c

We present our computational implementation of the spin-flip (SF) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and (full) triples (SDT) within Q-CHEM. The inclusion of triples not only enhances the quantitative accuracy of the SF-EOM-CCSD method but also provides correct qualitative trends in the energy gaps between strongly degenerate states. To assess the accuracy, we compare our SF-EOM-CCSDT results with full configuration interaction (FCI) and complete-active-space self-consistent field second-order (CASSCF-SO) CI benchmarks to study the adiabatic energy gaps in CH 2 and NH 2 + diradicals, vertical excitation energies in CH radicals and the bond dissociation of the HF molecule. We have implemented SF-EOM-CCSDT using both the conventional double precision (DP) and the single precision (SP) algorithms. The use of SP does not introduce any significant errors in energies and energy gaps, and, due to low cost (relative to DP), turns out to be a promising approach to widen the applicability of EOM-CCSDT to bigger molecules. We present our computational implementation of the spin-flip (SF) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and (full) triples (SDT) within Q-CHEM.