Implementation of the full CCSDT electronic structure model with tensor decompositions

TL;DR

This paper presents a tensor decomposition approach to implement the CCSDT electronic structure method more efficiently, reducing computational scaling from N^8 to approximately N^6 while maintaining high accuracy.

Contribution

The authors introduce a novel tensor decomposition technique for CCSDT that significantly lowers computational costs without sacrificing accuracy, enabling larger system calculations.

Findings

Achieved near N^6 scaling for CCSDT calculations.

Maintained 1 kJ/mol accuracy with reasonable SVD subspace sizes.

Validated method with benchmark calculations on small molecules.

Abstract

We report a complete implementation of the coupled-cluster method with single, double, and triple excitations (CCSDT) where tensor decompositions are used to reduce its scaling and overall computational costs. For the decomposition of the electron repulsion integrals the standard density fitting (or Cholesky decomposition) format is used. The coupled-cluster single and double amplitudes are treated conventionally, and for the triple amplitudes tensor we employ the Tucker-3 compression formula, $t_{ijk}^{abc} \approx t_{XYZ} \,U^X_{ai}\,U^Y_{bj} \,U^Z_{ck}$. The auxiliary quantities $U^X_{ai}$ come from singular value decomposition (SVD) of an approximate triple amplitudes tensor based on perturbation theory. The efficiency of the proposed method relies on an observation that the dimension of the "compressed" tensor $t_{XYZ}$ sufficient to deliver a constant relative accuracy of the correlation energy grows only linearly with the size of the system, $N$. This fact, combined with proper factorization of the coupled-cluster equations, leads to practically $N^6$ scaling of the computational costs of the proposed method, as illustrated numerically for linear alkanes with increasing chain length. This constitutes a considerable improvement over the $N^8$ scaling of the conventional (uncompressed) CCSDT theory. The accuracy of the proposed method is verified by benchmark calculations of total and relative energies for several small molecular systems and comparison with the exact CCSDT method. The accuracy levels of 1 kJ/mol are easily achievable with reasonable SVD subspace size, and even more demanding levels of accuracy can be reached with a considerable reduction of the computational costs. Extensions of the proposed method to include higher excitations are briefly discussed, along with possible strategies of reducing other residual errors.