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

Pathak, Shivesh; Wagner, Lucas K.

doi:10.1063/1.5052906

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

Journal Article · Wed Dec 19 00:00:00 EST 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5052906· OSTI ID:1611136

Pathak, Shivesh ^[1];

^[1]

Univ. of Illinois at Urbana-Champaign, IL (United States)

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.

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Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: SC0008692; FG02-12ER46875

OSTI ID:: 1611136

Journal Information:: Journal of Chemical Physics, Vol. 149, Issue 23; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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