Non-orthogonal determinants in multi-Slater-Jastrow trial wave functions for fixed-node diffusion Monte Carlo

Shivesh Pathak, Lucas K. Wagner

Research output: Contribution to journalArticle

Abstract

The accuracy and efficiency of ab initio Quantum Monte Carlo (QMC) algorithms benefit greatly from compact variational trial wave functions that accurately reproduce ground state properties of a system. We investigate the possibility of using multi-Slater-Jastrow trial wave functions with non-orthogonal determinants by optimizing identical single particle orbitals independently in separate determinants. As a test case, we compute variational and fixed-node diffusion Monte Carlo (FN-DMC) energies of a C2 molecule. For a given multi-determinant expansion, we find that this non-orthogonal orbital optimization results in a consistent improvement in the variational energy and the FN-DMC energy on the order of a few tenths of an eV. In some cases, fewer non-orthogonal determinants are required compared to orthogonal ones in order to achieve similar accuracy in FN-DMC. Our calculations indicate that trial wave functions with non-orthogonal determinants can improve computed energies in a QMC calculation when compared to their orthogonal counterparts.

Original languageEnglish (US)
Article number234104
JournalJournal of Chemical Physics
Volume149
Issue number23
DOIs
StatePublished - Dec 21 2018

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Wave functions
determinants
wave functions
Ground state
orbitals
energy
Molecules
optimization
expansion
ground state
molecules

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Non-orthogonal determinants in multi-Slater-Jastrow trial wave functions for fixed-node diffusion Monte Carlo. / Pathak, Shivesh; Wagner, Lucas K.

In: Journal of Chemical Physics, Vol. 149, No. 23, 234104, 21.12.2018.

Research output: Contribution to journalArticle

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