FNO-CCSDTQ(5)$_\Lambda$ as an economical alternative for connected quintuple excitations contributions in coupled cluster thermochemistry

TL;DR

The paper proposes FNO-CCSDTQ(5)$_\Lambda$ as a computationally efficient method to approximate connected quintuple excitations in coupled cluster thermochemistry, achieving rapid convergence with low-cost cutoffs.

Contribution

It introduces a frozen natural orbital approach for connected quintuple excitations that reduces computational cost while maintaining accuracy in thermochemical calculations.

Findings

FNO-CCSDTQ(5)$_\Lambda$ with low cutoffs is a viable alternative to full calculations.

Rapid convergence of the FNO expansion for differential quintuple contributions.

Slower FNO convergence observed for second-row compounds.

Abstract

Contributions from connected quintuple excitations in coupled cluster theory can reach the 0.5 kcal/mol range, important enough to matter in accurate computational thermochemistry, yet the very steep $\propto N^{12}$ CPU time scaling impedes routine evaluation. We show that for the differential contribution of quintuples, convergence of a frozen natural orbital (FNO) expansion with respect to the NO cutoff is rapid enough to make FNO-CCSDTQ(5)$_\Lambda$ with cutoffs of 0.0025 or 0.001 viable alternatives. A naive extrapolation to zero cutoff from \{0.005,0.0025\} works surprisingly well as a low-cost option. Interestingly, FNO convergence is definitely slower for second-row than for first-row compounds.