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Title: High Accuracy Transition Metal Effective Cores for the Many-Body Diffusion Monte Carlo Method

Abstract

Practical applications of the real-space diffusion Monte Carlo (DMC) method require the removal of core electrons, where currently localization approximations of semilocal potentials are generally used in the projector. Accurate calculations of complex solids and large molecules demand minimizing the impact of approximated atomic cores. Prior works have shown that the errors from such approximations can be sizable in both finite and periodic systems. In this work, we show that a class of differential pseudopotentials, known as pseudo-Hamiltonians, can be constructed for the 3d transition metal atoms, entirely removing the need for any localization scheme in the DMC projector. As a proof of principle, we demonstrate the approach for the case of Co. In order to minimize errors in the pseudo-Hamiltonian at the many-body level, we generalize the recently proposed correlation-consistent pseudopotential generation scheme to successively close semilocal representations of the differential potentials. Our generation scheme successfully produces potentials tailored specifically for real space projector quantum Monte Carlo methods with low error at the many-body level, i.e., with many-body scattering properties very close to relativistic all-electron results. In particular, we show that the agreement with respect to atomic and molecular quantities reach chemical accuracy in many cases-on par with themore » most accurate semilocal pseudopotentials available. Further, our pseudo-Hamiltonian generation scheme utilizes standard quantum chemistry codes designed only to work with semilocal pseudopotentials, enabling straightforward generation of pseudo-Hamiltonians for additional elements in future works.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
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  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. North Carolina State Univ., Raleigh, NC (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
OSTI Identifier:
1842606
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 18; Journal Issue: 2; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Pseudopotentials; Optimization; Energy; Quantum mechanics; Approximation

Citation Formats

Bennett, Chandler, Reboredo, Fernando A., Mitas, Lubos, and Krogel, Jaron. High Accuracy Transition Metal Effective Cores for the Many-Body Diffusion Monte Carlo Method. United States: N. p., 2022. Web. doi:10.1021/acs.jctc.1c00992.
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Bennett, Chandler, Reboredo, Fernando A., Mitas, Lubos, & Krogel, Jaron. High Accuracy Transition Metal Effective Cores for the Many-Body Diffusion Monte Carlo Method. United States. https://doi.org/10.1021/acs.jctc.1c00992
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Bennett, Chandler, Reboredo, Fernando A., Mitas, Lubos, and Krogel, Jaron. Mon . "High Accuracy Transition Metal Effective Cores for the Many-Body Diffusion Monte Carlo Method". United States. https://doi.org/10.1021/acs.jctc.1c00992. https://www.osti.gov/servlets/purl/1842606.
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@article{osti_1842606,
title = {High Accuracy Transition Metal Effective Cores for the Many-Body Diffusion Monte Carlo Method},
author = {Bennett, Chandler and Reboredo, Fernando A. and Mitas, Lubos and Krogel, Jaron},
abstractNote = {Practical applications of the real-space diffusion Monte Carlo (DMC) method require the removal of core electrons, where currently localization approximations of semilocal potentials are generally used in the projector. Accurate calculations of complex solids and large molecules demand minimizing the impact of approximated atomic cores. Prior works have shown that the errors from such approximations can be sizable in both finite and periodic systems. In this work, we show that a class of differential pseudopotentials, known as pseudo-Hamiltonians, can be constructed for the 3d transition metal atoms, entirely removing the need for any localization scheme in the DMC projector. As a proof of principle, we demonstrate the approach for the case of Co. In order to minimize errors in the pseudo-Hamiltonian at the many-body level, we generalize the recently proposed correlation-consistent pseudopotential generation scheme to successively close semilocal representations of the differential potentials. Our generation scheme successfully produces potentials tailored specifically for real space projector quantum Monte Carlo methods with low error at the many-body level, i.e., with many-body scattering properties very close to relativistic all-electron results. In particular, we show that the agreement with respect to atomic and molecular quantities reach chemical accuracy in many cases-on par with the most accurate semilocal pseudopotentials available. Further, our pseudo-Hamiltonian generation scheme utilizes standard quantum chemistry codes designed only to work with semilocal pseudopotentials, enabling straightforward generation of pseudo-Hamiltonians for additional elements in future works.},
doi = {10.1021/acs.jctc.1c00992},
journal = {Journal of Chemical Theory and Computation},
number = 2,
volume = 18,
place = {United States},
year = {Mon Jan 10 00:00:00 EST 2022},
month = {Mon Jan 10 00:00:00 EST 2022}
}
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https://doi.org/10.1021/acs.jctc.1c00992
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