A correctly scaling rigorously spin-adapted and spin-complete open-shell CCSD implementation for arbitrary high-spin states

TL;DR

This paper introduces a novel, correctly scaling CCSD implementation for high-spin open-shell states that ensures spin completeness and purity using a spin-free cluster operator and advanced tensor contraction techniques.

Contribution

It presents a new spin-adapted, spin-complete CCSD method employing second quantization and tensor contractions, improving accuracy for high-spin open-shell systems.

Findings

SASC-CCSD shows reasonable convergence for small molecules.

SASC-CCSD yields slightly improved correlation energies over spin orbital CCSD.

Differences in correlation energies are up to 0.886 mE_H (0.98%).

Abstract

In this paper, we report on a correctly scaling novel coupled cluster singles and doubles (CCSD) implementation for arbitrary high-spin open-shell states. The chosen cluster operator is completely spin-free, i.e. employs spatial substitutions only. It is composed of our recently developed L\"owdin-type operators (doi: 10.1063/5.0026762), which ensure (1) spin completeness and (2) spin adaption i.e. spin purity of the CC wave function. In contrast to the proof-of-concept matrix-representation-based implementation presented there, the present implementation relies on second quantization and factorized tensor contractions. The generated singles and doubles operators are embedded in an equation generation engine. In the latter, Wick's theorem is used to derive prefactors arising from spin integration directly from the spin-free full contraction patterns. The obtained Wick terms composed of products of Kronecker deltas are represented by special non-antisymmetrized Goldstone diagrams. Identical (redundant) diagrams are identified by solving the underlying graph isomorphism problem. All non-redundant graphs are then automatically translated to locally -- one term at a time -- factorized tensor contractions. Finally, the spin-adapted and spin-complete (SASC) CCS and CCSD variants are applied to a set of small molecular test systems. Both correlation energies and amplitude norms hint towards a reasonable convergence of the SASC-CCSD method for a BCH series truncation of order four. In comparison to spin orbital CCSD, SASC-CCSD leads to slightly improved correlation energies with differences of up to 0.886 mE_H (0.98% w.r.t. spin orbital CCSD(T)).