Doubly Occupied Pair Coupled Cluster F12 Approach

• Published in: Journal of chemical theory and computation 2020-12, Vol.16 (12), p.7372-7380
• Main Authors: Kedžuch, Stanislav, Šimunek, Ján, Veis, Matej, Noga, Jozef
• Format: Article
• Language: English
• Subjects: Clusters; Correlation coefficients; Coupling (molecular); Enthalpy; Excitation; Hydrogen atoms; Molecular orbitals; Quantum Electronic Structure; Wave functions
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.0c00659

Inspired by reports of the good performance of the doubly occupied pair coupled cluster (pCCD) theory in describing static electron correlation, we have introduced and implemented a variant thereof that includes single excitations and explicitly treats the dynamic electron correlation using the F12 methodology (pCCSD-F12). This drastically reduces the computation scaling with respect to the standard method using the full double-excitation operator (CCSD-F12). Slater-type geminals as a correlation factor, together with fixed cusp conditions, were used, which is known as the SP-ansatz. For sample model systems, we have investigated the performance of reference states constructed from either canonical or localized molecular orbitals. Finaly, the employment of Brueckner orbitals has been tested, which causes the single excitations to naturally vanish from the wave function expansion (B-pCCD-F12). Our test systems include different-sized rings of hydrogen atoms and dissociation curves for small molecules such as HF, N2, and CO2; and comparison with CCSD-F12 is presented for a series of reaction enthalpies.