Tensor-decomposed vibrational coupled-cluster theory: Enabling large-scale, highly accurate vibrational-structure calculations.

Abstract

A new implementation of vibrational coupled-cluster (VCC) theory is presented, where all amplitude tensors are represented in the canonical polyadic (CP) format. The CP-VCC algorithm solves the non-linear VCC equations without ever constructing the amplitudes or error vectors in full dimension but still formally includes the full parameter space of the VCC[n] model in question resulting in the same vibrational energies as the conventional method. In a previous publication, we have described the non-linear-equation solver for CP-VCC calculations. In this work, we discuss the general algorithm for evaluating VCC error vectors in CP format including the rank-reduction methods used during the summation of the many terms in the VCC amplitude equations. Benchmark calculations for studying the computational scaling and memory usage of the CP-VCC algorithm are performed on a set of molecules including thiadiazole and an array of polycyclic aromatic hydrocarbons. The results show that the reduced scaling and memory requirements of the CP-VCC algorithm allows for performing high-order VCC calculations on systems with up to 66 vibrational modes (anthracene), which indeed are not possible using the conventional VCC method. This paves the way for obtaining highly accurate vibrational spectra and properties of larger molecules.