Connected three-body terms in single-reference unitary many-body theories: Iterative and perturbative approximations

TL;DR

This paper develops and compares iterative and perturbative methods to include connected three-body terms in unitary many-body theories, notably improving accuracy over traditional coupled cluster methods for molecular energies.

Contribution

It introduces new approximate LDSRG(3) models and perturbative triples corrections that enhance accuracy while reducing computational cost in many-body quantum chemistry calculations.

Findings

LDSRG(3)-2 outperforms CCSDT in correlation energy accuracy.

qDSRG(2)+(T) matches CCSD(T) accuracy for small molecules.

New methods are computationally feasible and improve energetic predictions.

Abstract

This work introduces various approaches to include connected three-body terms in unitary many-body theories, focusing a representative example on the driven similarity renormalization group (DSRG). Starting from the least approximate method - the linearized DSRG truncated to one-, two-, and three-body operators [LDSRG(3)] - we develop several approximate LDSRG(3) models with reduced computational cost. Through a perturbative analysis, we motivate a family of iterative LDSRG(3)-$n$ and -$n'$ ($n=1,2,3,4$) methods that contain a subset of the LDSRG(3) diagrams. Among these variants, the LDSRG(3)-2 scheme has the same computational complexity of coupled cluster theory with singles, doubles, and triples (CCSDT), but it outperforms CCSDT in the accuracy of the predicted correlation energies. We also propose and implement two perturbative triples corrections based on the linearized DSRG truncated to one- and two-body operators augmented with recursive quadratic commutators [qDSRG(2)]. The resulting qDSRG(2)+(T) approach matches the accuracy of the "gold-standard" coupled cluster theory with singles, doubles, and perturbative triples model on the energetics of twenty-eight closed-shell atoms and small molecules.