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

Journal Article · · Physical Review B
 [1];  [2];  [1];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Diffusion Monte Carlo (DMC) calculations of the spectroscopic properties of a large set of molecules were performed, assessing the effect of different approximations. In systems containing elements with large atomic numbers, we show that the errors associated with the use of nonlocal mean-field-based pseudopotentials in DMC calculations can be significant and may surpass the fixed-node error. We suggest practical guidelines for reducing these pseudopotential errors, which allow us to obtain DMC-computed spectroscopic parameters of molecules and equation of state properties of solids in excellent agreement with experiment.
Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA; Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC04-94AL85000; AC05-00OR22725; AC52-07NA27344
OSTI ID:
1261352
Alternate ID(s):
OSTI ID: 1244158
OSTI ID: 1262188
Report Number(s):
LLNL-JRNL--676682; KC0202030; ERKCK03
Journal Information:
Physical Review B, Journal Name: Physical Review B Journal Issue: 9 Vol. 93; ISSN 2469-9950
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (90)

An Introduction to the Bootstrap book January 1993
Potential energy curves and dissociation energies of NbO, SiC, CP, PH+, SiF+, and NH+ journal January 1992
The statistical error of green's function Monte Carlo journal June 1986
Fully relativistic correlated benchmark results for uranyl and a critical look at relativistic effective core potentials for uranium
  • de Jong, W. A.; Harrison, R. J.; Nichols, J. A.
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 107, Issue 1 https://doi.org/10.1007/s002140100293
journal December 2001
A new determinant-based full configuration interaction method journal November 1984
The bond length of silver dimer journal November 1991
On the electronic spectrum of the Mo2 molecule observed after flash photolysis of Mo(CO)6 journal December 1978
Analysis of the E-X and C-X band system isotopically enriched of Ag2 journal November 1981
Potential-energy functions of diatomic molecules of the noble gases I. Like nuclear species journal October 1992
The crystal dynamics of grey (α) tin at 90°K journal October 1969
Atomic-environment classification of the chemical elements journal June 1993
Relativistic Pseudopotentials: Their Development and Scope of Applications journal September 2011
Effective Core Potentials for DFT Calculations journal November 1995
Comparison of Density Functional and MP2 Calculations on the Water Monomer and Dimer journal October 1994
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields journal November 1994
Towards an exact description of electronic wavefunctions in real solids journal December 2012
Dissociation energy and excited-state properties of diatomic Sn2 journal January 1988
Hybrid functionals based on a screened Coulomb potential journal May 2003
Dissociation Energy of Pd 2 journal September 1969
Thermodynamic investigation of the gaseous molecules TiRh, Rh 2 , and Ti 2 Rh by mass spectrometry journal March 1974
Norm-conserving Hartree–Fock pseudopotentials and their asymptotic behavior journal January 2005
Smooth relativistic Hartree–Fock pseudopotentials for H to Ba and Lu to Hg journal May 2005
Energy-consistent pseudopotentials for quantum Monte Carlo calculations journal June 2007
Energy-consistent small-core pseudopotentials for 3d-transition metals adapted to quantum Monte Carlo calculations journal October 2008
Electron structure calculations including CI for ten low lying states of Pb 2 and Sn 2 . Partition function and dissociation energy of Sn 2 journal January 1983
Electronic structure and bonding in the Pd 2 molecule by all electron a b i n i t i o HF–CI calculations and mass spectrometric measurements journal May 1984
Valence quantum Monte Carlo with a b i n i t i o effective core potentials journal July 1987
Nonlocal pseudopotentials and diffusion Monte Carlo journal September 1991
Spectroscopy of mass‐selected tantalum dimers in argon matrices journal June 1992
Simulated annealing study of neutral and charged clusters: Al n and Ga n journal July 1993
Spectroscopy of mass-selected rhodium dimers in argon matrices journal February 1997
Photoionization spectroscopy of dichromium and dimolybdenum: Ionization potentials and bond energies journal June 1998
A soft Hartree–Fock pseudopotential for carbon with application to quantum Monte Carlo journal August 1998
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
Pseudopotentials for correlated electron systems journal July 2013
Correlated electron pseudopotentials for 3d-transition metals journal February 2015
The Compressibility of Media under Extreme Pressures journal September 1944
Error Estimates for Solid-State Density-Functional Theory Predictions: An Overview by Means of the Ground-State Elemental Crystals journal October 2013
A universal equation of state for solids journal July 1986
Applications of quantum Monte Carlo methods in condensed systems journal January 2011
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials journal September 2009
Continuum variational and diffusion quantum Monte Carlo calculations journal December 2009
Improved semiconductor lattice parameters and band gaps from a middle-range screened hybrid exchange functional journal March 2012
New Method for Calculating Wave Functions in Crystals and Molecules journal October 1959
Diatomic Molecules According to the Wave Mechanics. II. Vibrational Levels journal July 1929
Improved Pauli Hamiltonian for local-potential problems journal September 1978
Self-interaction correction to density-functional approximations for many-electron systems journal May 1981
Variational quantum Monte Carlo nonlocal pseudopotential approach to solids: Formulation and application to diamond, graphite, and silicon journal August 1990
Efficient pseudopotentials for plane-wave calculations journal January 1991
Erratum: Variational quantum Monte Carlo nonlocal pseudopotential approach to solids: Formulation and application to diamond, graphite, and silicon journal April 1991
Effects of three-body and backflow correlations in the two-dimensional electron gas journal October 1993
Finite-size effects and Coulomb interactions in quantum Monte Carlo calculations for homogeneous systems with periodic boundary conditions journal January 1996
Elimination of Coulomb finite-size effects in quantum many-body simulations journal February 1997
Finite-size errors in quantum many-body simulations of extended systems journal January 1999
Transferable relativistic Dirac-Slater pseudopotentials journal July 2000
Chemically Motivated Pseudopotential for Sodium journal February 1973
Efficient localized basis set for quantum Monte Carlo calculations on condensed matter journal October 2004
Jastrow correlation factor for atoms, molecules, and solids journal December 2004
Variance-minimization scheme for optimizing Jastrow factors journal August 2005
Beyond the locality approximation in the standard diffusion Monte Carlo method journal October 2006
Electronic surface error in the Si interstitial formation energy journal April 2008
Finite-size errors in continuum quantum Monte Carlo calculations journal September 2008
Quantum Monte Carlo study of circular quantum dots in presence of Rashba interaction journal April 2011
Temperature-driven phase transitions from first principles including all relevant excitations: The fcc-to-bcc transition in Ca journal December 2011
Diffusion quantum Monte Carlo study of the equation of state and point defects in aluminum journal April 2012
Vacancy formation energies in fcc metals: Influence of exchange-correlation functionals and correction schemes journal April 2012
Quantum Monte Carlo applied to solids journal December 2013
Twist-averaged boundary conditions in continuum quantum Monte Carlo algorithms journal June 2001
Inhomogeneous backflow transformations in quantum Monte Carlo calculations journal December 2006
Finite-Size Correction in Many-Body Electronic Structure Calculations journal March 2008
Norm-Conserving Pseudopotentials journal November 1979
Ground State of the Electron Gas by a Stochastic Method journal August 1980
Efficacious Form for Model Pseudopotentials journal May 1982
Variational Quantum Monte Carlo Nonlocal Pseudopotential Approach to Solids: Cohesive and Structural Properties of Diamond journal October 1988
New stochastic method for systems with broken time-reversal symmetry: 2D fermions in a magnetic field journal October 1993
Generalized Gradient Approximation Made Simple journal October 1996
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] journal February 1997
Reptation Quantum Monte Carlo: A Method for Unbiased Ground-State Averages and Imaginary-Time Correlations journal June 1999
Vacancies in Metals: From First-Principles Calculations to Experimental Data journal October 2000
Linear-Scaling Quantum Monte Carlo Calculations journal November 2001
Quantum Monte Carlo Method using Phase-Free Random Walks with Slater Determinants journal April 2003
Van der Waals Density Functional for General Geometries journal June 2004
Finite-Size Error in Many-Body Simulations with Long-Range Interactions journal August 2006
Ab initio Quantum Monte Carlo Calculations of Spin Superexchange in Cuprates: The Benchmarking Case of Ca 2 CuO 3 journal July 2014
Recent progress in the field of electron correlation journal April 1994
Path integrals in the theory of condensed helium journal April 1995
Quantum Monte Carlo simulations of solids journal January 2001
Continuous-time Monte Carlo methods for quantum impurity models journal May 2011
Accelerating Quantum Monte Carlo Simulations of Real Materials on GPU Clusters journal January 2012
Architecture of Qbox: A scalable first-principles molecular dynamics code journal January 2008

Cited By (12)

Cohesive energy and structural parameters of binary oxides of groups IIA and IIIB from diffusion quantum Monte Carlo journal May 2016
Quantum Monte Carlo with variable spins journal June 2016
Accurate barrier heights using diffusion Monte Carlo journal March 2017
Magnitude of pseudopotential localization errors in fixed node diffusion quantum Monte Carlo journal June 2017
Quantitative estimation of localization errors of 3 d transition metal pseudopotentials in diffusion Monte Carlo journal July 2017
A new generation of effective core potentials for correlated calculations journal December 2017
A new generation of effective core potentials from correlated calculations: 2nd row elements journal September 2018
Auxiliary-field quantum Monte Carlo calculations of the structural properties of nickel oxide journal October 2018
Auxiliary-field quantum Monte Carlo calculations with multiple-projector pseudopotentials journal April 2017
Cohesive energy and structural parameters of binary oxides of groups IIA and IIIB from diffusion quantum Monte Carlo text January 2016
Auxiliary-field quantum Monte Carlo calculations with multiple-projector pseudopotentials text January 2016
Magnitude of pseudopotential localization errors in fixed node diffusion quantum Monte Carlo text January 2017

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