Low-rank canonical-tensor decomposition of potential energy surfaces: application to grid-based diagrammatic vibrational Green’s function theory

Prashant Rai, Khachik Sargsyan, Habib Najm, Matthew R. Hermes, So Hirata

Research output: Contribution to journalArticle

Abstract

A new method is proposed for a fast evaluation of high-dimensional integrals of potential energy surfaces (PES) that arise in many areas of quantum dynamics. It decomposes a PES into a canonical low-rank tensor format, reducing its integral into a relatively short sum of products of low-dimensional integrals. The decomposition is achieved by the alternating least squares (ALS) algorithm, requiring only a small number of single-point energy evaluations. Therefore, it eradicates a force-constant evaluation as the hotspot of many quantum dynamics simulations and also possibly lifts the curse of dimensionality. This general method is applied to the anharmonic vibrational zero-point and transition energy calculations of molecules using the second-order diagrammatic vibrational many-body Green's function (XVH2) theory with a harmonic-approximation reference. In this application, high dimensional PES and Green's functions are both subjected to a low-rank decomposition. Evaluating the molecular integrals over a low-rank PES and Green's functions as sums of low-dimensional integrals using the Gauss–Hermite quadrature, this canonical-tensor-decomposition-based XVH2 (CT-XVH2) achieves an accuracy of 0.1 cm−1 or higher and nearly an order of magnitude speedup as compared with the original algorithm using force constants for water and formaldehyde.

Original languageEnglish (US)
Pages (from-to)2120-2134
Number of pages15
JournalMolecular Physics
Volume115
Issue number17-18
DOIs
StatePublished - Sep 17 2017

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Keywords

  • Green's function theory
  • Potential energy surfaces
  • anharmonic vibrations
  • tensor decomposition

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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