When gold is not enough: platinum standard of quantum chemistry with $N^7$ cost

TL;DR

This paper introduces a rank-reduced coupled-cluster method for non-iterative quadruple excitation energy corrections with a computational cost scaling as N^7, achieving high accuracy for small molecules and complex rearrangement energies.

Contribution

It extends coupled-cluster formalism with Tucker format compression and a modified functional, enabling efficient and accurate quadruple excitation energy corrections with minimal additional parameters.

Findings

Cost scales as N^7, making it feasible for larger systems.

Achieves a few percent accuracy in energy corrections.

Successfully applied to isomerization and rearrangement energies.

Abstract

In this paper we extend the rank-reduced coupled-cluster formalism to the calculation of non-iterative energy corrections due to quadruple excitations. There are two major components of the proposed formalism. The first is an approximate compression of the quadruple excitation amplitudes using the Tucker format. The second is a modified functional used for evaluation of the corrections which gives exactly the same results for the exact amplitudes, but is less susceptible to errors resulting from the aforementioned compression. We show, both theoretically and numerically, that the computational cost of the proposed method scales as the seventh power of the system size. Using reference results for a set of small molecules, the method is calibrated to deliver relative accuracy of a few percent in energy corrections. To illustrate the potential of the theory we calculate the isomerization energy of \emph{ortho}/\emph{meta} benzyne (C$_6$H$_4$) and the barrier height for the Cope rearrangement in bullvalene (C$_{10}$H$_{10}$). The method retains a near-black-box nature of the conventional coupled-cluster formalism and depends on only one additional parameter that controls the accuracy.