Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Quantitative estimation of localization errors of 3d transition metal pseudopotentials in diffusion Monte Carlo

Abstract

The necessarily approximate evaluation of non-local pseudopotentials in diffusion Monte Carlo (DMC) introduces localization errors. In this paper, we estimate these errors for two families of non-local pseudopotentials for the first-row transition metal atoms Sc–Zn using an extrapolation scheme and multideterminant wavefunctions. Sensitivities of the error in the DMC energies to the Jastrow factor are used to estimate the quality of two sets of pseudopotentials with respect to locality error reduction. The locality approximation and T-moves scheme are also compared for accuracy of total energies. After estimating the removal of the locality and T-moves errors, we present the range of fixed-node energies between a single determinant description and a full valence multideterminant complete active space expansion. The results for these pseudopotentials agree with previous findings that the locality approximation is less sensitive to changes in the Jastrow than T-moves yielding more accurate total energies, however not necessarily more accurate energy differences. For both the locality approximation and T-moves, we find decreasing Jastrow sensitivity moving left to right across the series Sc–Zn. The recently generated pseudopotentials of Krogel et al. reduce the magnitude of the locality error compared with the pseudopotentials of Burkatzki et al. by an average estimated 40% usingmore » the locality approximation. The estimated locality error is equivalent for both sets of pseudopotentials when T-moves is used. Finally, for the Sc–Zn atomic series with these pseudopotentials, and using up to three-body Jastrow factors, our results suggest that the fixed-node error is dominant over the locality error when a single determinant is used.« less

Authors:
 [1];  [1];  [1]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1376434
Alternate Identifier(s):
OSTI ID: 1368604
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electronic structure calculations; Metalloids; Monte Carlo methods; Wave functions; Matrix theory

Citation Formats

Dzubak, Allison L., Krogel, Jaron T., and Reboredo, Fernando A. Quantitative estimation of localization errors of 3d transition metal pseudopotentials in diffusion Monte Carlo. United States: N. p., 2017. Web. doi:10.1063/1.4991414.
Copy to clipboard
Dzubak, Allison L., Krogel, Jaron T., & Reboredo, Fernando A. Quantitative estimation of localization errors of 3d transition metal pseudopotentials in diffusion Monte Carlo. United States. https://doi.org/10.1063/1.4991414
Copy to clipboard
Dzubak, Allison L., Krogel, Jaron T., and Reboredo, Fernando A. Mon . "Quantitative estimation of localization errors of 3d transition metal pseudopotentials in diffusion Monte Carlo". United States. https://doi.org/10.1063/1.4991414. https://www.osti.gov/servlets/purl/1376434.
Copy to clipboard
@article{osti_1376434,
title = {Quantitative estimation of localization errors of 3d transition metal pseudopotentials in diffusion Monte Carlo},
author = {Dzubak, Allison L. and Krogel, Jaron T. and Reboredo, Fernando A.},
abstractNote = {The necessarily approximate evaluation of non-local pseudopotentials in diffusion Monte Carlo (DMC) introduces localization errors. In this paper, we estimate these errors for two families of non-local pseudopotentials for the first-row transition metal atoms Sc–Zn using an extrapolation scheme and multideterminant wavefunctions. Sensitivities of the error in the DMC energies to the Jastrow factor are used to estimate the quality of two sets of pseudopotentials with respect to locality error reduction. The locality approximation and T-moves scheme are also compared for accuracy of total energies. After estimating the removal of the locality and T-moves errors, we present the range of fixed-node energies between a single determinant description and a full valence multideterminant complete active space expansion. The results for these pseudopotentials agree with previous findings that the locality approximation is less sensitive to changes in the Jastrow than T-moves yielding more accurate total energies, however not necessarily more accurate energy differences. For both the locality approximation and T-moves, we find decreasing Jastrow sensitivity moving left to right across the series Sc–Zn. The recently generated pseudopotentials of Krogel et al. reduce the magnitude of the locality error compared with the pseudopotentials of Burkatzki et al. by an average estimated 40% using the locality approximation. The estimated locality error is equivalent for both sets of pseudopotentials when T-moves is used. Finally, for the Sc–Zn atomic series with these pseudopotentials, and using up to three-body Jastrow factors, our results suggest that the fixed-node error is dominant over the locality error when a single determinant is used.},
doi = {10.1063/1.4991414},
journal = {Journal of Chemical Physics},
number = 2,
volume = 147,
place = {United States},
year = {Mon Jul 10 00:00:00 EDT 2017},
month = {Mon Jul 10 00:00:00 EDT 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.4991414
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Relativistic effective potentials in quantum Monte Carlo calculations
journal, January 1987

  • Hurley, M. M.; Christiansen, P. A.
  • The Journal of Chemical Physics, Vol. 86, Issue 2
  • DOI: 10.1063/1.452294

Size-consistent variational approaches to nonlocal pseudopotentials: Standard and lattice regularized diffusion Monte Carlo methods revisited
journal, April 2010

  • Casula, Michele; Moroni, Saverio; Sorella, Sandro
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3380831

Monte-Carlo solution of Schrödinger's equation
journal, February 1971

Quantum Monte Carlo applied to solids
journal, December 2013

A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980

Benchmarking the pseudopotential and fixed-node approximations in diffusion Monte Carlo calculations of molecules and solids
journal, March 2016

Towards a systematic assessment of errors in diffusion Monte Carlo calculations of semiconductors: Case study of zinc selenide and zinc oxide
journal, December 2015

  • Yu, Jaehyung; Wagner, Lucas K.; Ertekin, Elif
  • The Journal of Chemical Physics, Vol. 143, Issue 22
  • DOI: 10.1063/1.4937421

Diffusion Monte Carlo for Accurate Dissociation Energies of 3d Transition Metal Containing Molecules
journal, May 2016

  • Doblhoff-Dier, Katharina; Meyer, Jörg; Hoggan, Philip E.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 6
  • DOI: 10.1021/acs.jctc.6b00160

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

A random‐walk simulation of the Schrödinger equation: H + 3
journal, August 1975

  • Anderson, James B.
  • The Journal of Chemical Physics, Vol. 63, Issue 4
  • DOI: 10.1063/1.431514

Quantum chemistry by random walk. H 2 P , H + 3 D 3 h 1 A ′ 1 , H 2 3 Σ + u , H 4 1 Σ + g , Be 1 S
journal, November 1976

  • Anderson, James B.
  • The Journal of Chemical Physics, Vol. 65, Issue 10
  • DOI: 10.1063/1.432868

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Smooth relativistic Hartree–Fock pseudopotentials for H to Ba and Lu to Hg
journal, May 2005

  • Trail, J. R.; Needs, R. J.
  • The Journal of Chemical Physics, Vol. 122, Issue 17
  • DOI: 10.1063/1.1888569

Ab initio Quantum Monte Carlo Calculations of Spin Superexchange in Cuprates: The Benchmarking Case of Ca 2 CuO 3
journal, July 2014

Erratum: Alleviation of the Fermion-Sign Problem by Optimization of Many-Body Wave Functions [Phys. Rev. Lett. 98 , 110201 (2007)]
journal, October 2007

Phase stability and properties of manganese oxide polymorphs: Assessment and insights from diffusion Monte Carlo
journal, December 2015

Hybrid algorithms in quantum Monte Carlo
journal, December 2012

Ground state of doped cuprates from first-principles quantum Monte Carlo calculations
journal, October 2015

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

Probing the accuracy of pseudopotentials for transition metals in quantum Monte Carlo calculations
journal, November 1997

  • Flad, Heinz-Jürgen; Dolg, Michael
  • The Journal of Chemical Physics, Vol. 107, Issue 19
  • DOI: 10.1063/1.475055

The Nature of the Interlayer Interaction in Bulk and Few-Layer Phosphorus
journal, November 2015

Nonlocal pseudopotentials and diffusion Monte Carlo
journal, September 1991

  • Mitáš, Luboš; Shirley, Eric L.; Ceperley, David M.
  • The Journal of Chemical Physics, Vol. 95, Issue 5
  • DOI: 10.1063/1.460849

Discovering correlated fermions using quantum Monte Carlo
journal, August 2016

Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo
journal, April 2015

  • Santana, Juan A.; Krogel, Jaron T.; Kim, Jeongnim
  • The Journal of Chemical Physics, Vol. 142, Issue 16
  • DOI: 10.1063/1.4919242

Competing collinear magnetic structures in superconducting FeSe by first-principles quantum Monte Carlo calculations
journal, July 2016

Norm-conserving Hartree–Fock pseudopotentials and their asymptotic behavior
journal, January 2005

  • Trail, J. R.; Needs, R. J.
  • The Journal of Chemical Physics, Vol. 122, Issue 1
  • DOI: 10.1063/1.1829049

Theory of finite size effects for electronic quantum Monte Carlo calculations of liquids and solids
journal, July 2016

Computation of the Correlated Metal-Insulator Transition in Vanadium Dioxide from First Principles
journal, April 2015

Magnitude of pseudopotential localization errors in fixed node diffusion quantum Monte Carlo
journal, June 2017

  • Krogel, Jaron T.; Kent, P. R. C.
  • The Journal of Chemical Physics, Vol. 146, Issue 24
  • DOI: 10.1063/1.4986951

Energy-consistent small-core pseudopotentials for 3d-transition metals adapted to quantum Monte Carlo calculations
journal, October 2008

  • Burkatzki, M.; Filippi, Claudia; Dolg, M.
  • The Journal of Chemical Physics, Vol. 129, Issue 16
  • DOI: 10.1063/1.2987872

Many-body ab initio diffusion quantum Monte Carlo applied to the strongly correlated oxide NiO
journal, October 2015

  • Mitra, Chandrima; Krogel, Jaron T.; Santana, Juan A.
  • The Journal of Chemical Physics, Vol. 143, Issue 16
  • DOI: 10.1063/1.4934262

Equations of state and stability of MgSiO 3 perovskite and post-perovskite phases from quantum Monte Carlo simulations
journal, November 2014

Theory of melting at high pressures: Amending density functional theory with quantum Monte Carlo
journal, October 2014

Nexus: A modular workflow management system for quantum simulation codes
journal, January 2016

Point-defect optical transitions and thermal ionization energies from quantum Monte Carlo methods: Application to the F -center defect in MgO
journal, April 2013

Approximate and exact nodes of fermionic wavefunctions: Coordinate transformations and topologies
journal, August 2005

Cohesive energy and structural parameters of binary oxides of groups IIA and IIIB from diffusion quantum Monte Carlo
journal, May 2016

  • Santana, Juan A.; Krogel, Jaron T.; Kent, Paul R. C.
  • The Journal of Chemical Physics, Vol. 144, Issue 17
  • DOI: 10.1063/1.4947569

Self-healing diffusion quantum Monte Carlo algorithms: Direct reduction of the fermion sign error in electronic structure calculations
journal, May 2009

Fermion nodes
journal, June 1991

  • Ceperley, D. M.
  • Journal of Statistical Physics, Vol. 63, Issue 5-6
  • DOI: 10.1007/bf01030009

Many-Body Problem with Strong Forces
journal, June 1955

Pfaffian pairing and backflow wavefunctions for electronic structure quantum Monte Carlo methods
journal, March 2008

Theory of melting at high pressures: Amending Density Functional Theory with Quantum Monte Carlo
text, January 2013

The Nature of the Interlayer Interaction in Bulk and Few-Layer Phosphorus
text, January 2015

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    An efficient hybrid orbital representation for quantum Monte Carlo calculations
    journal, August 2018

    • Luo, Ye; Esler, Kenneth P.; Kent, Paul R. C.
    • The Journal of Chemical Physics, Vol. 149, Issue 8
    • DOI: 10.1063/1.5037094

    Reduced scaling Hilbert space variational Monte Carlo
    journal, November 2018

    • Wei, Haochuan; Neuscamman, Eric
    • The Journal of Chemical Physics, Vol. 149, Issue 18
    • DOI: 10.1063/1.5047207

    A new scheme for fixed node diffusion quantum Monte Carlo with pseudopotentials: Improving reproducibility and reducing the trial-wave-function bias
    journal, October 2019

    • Zen, Andrea; Brandenburg, Jan Gerit; Michaelides, Angelos
    • The Journal of Chemical Physics, Vol. 151, Issue 13
    • DOI: 10.1063/1.5119729

    Structural, electronic, and magnetic properties of bulk and epitaxial LaCoO 3 through diffusion Monte Carlo
    journal, December 2019

    An efficient hybrid orbital representation for quantum Monte Carlo calculations
    text, January 2018

    Reduced Scaling Hilbert Space Variational Monte Carlo
    text, January 2018

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: