Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

New generation of effective core potentials from correlated calculations: 2nd row elements

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5038135· OSTI ID:1441470
 [1];  [1];  [2];  [2];  [3];  [2]
  1. North Carolina State Univ., Raleigh, NC (United States). Department of Physics; Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. North Carolina State Univ., Raleigh, NC (United States). Department of Physics
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
+ Show Author Affiliations
Very recently, we have introduced correlation consistent effective core potentials (ccECPs) derived from many-body approaches with the main target being its use in explicitly correlated methods but also in mainstream approaches. The ccECPs are based on reproducing excitation energies for a subset of valence states, i.e., achieving a near-isospectrality between the original and pseudo Hamiltonians. Additionally, binding curves of dimer molecules have been used for refinement and overall improvement of transferability over a range of bond lengths. Here we apply similar ideas to the second row elements and study several aspects of the constructions in order to find the optimal (or nearly-optimal) solutions within the chosen ECP forms with 3s, 3p valence space (Ne-core). New constructions exhibit accurate low-lying atomic excitations and equilibrium molecular bonds (on average within ≈ 0.03 eV and 3 mA), however, the errors for A1 and Si oxide molecules at short bond lengths are notably larger for both ours and existing ECPs. Assuming this limitation, our ccECPs show a systematic balance between the criteria of atomic spectra accuracy and transferability for molecular bonds. Finally, in order to provide another option with much higher uniform accuracy, we also construct He-core ECPs for the whole row with typical discrepancies of ≈ 0.01 eV or smaller.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
AC04-94AL85000; NA0003525
OSTI ID:
1441470
Alternate ID(s):
OSTI ID: 1470794
Report Number(s):
SAND--2018-4735J; 662779
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 10 Vol. 149; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (65)

A new technique for inconsistent QP problems in the SQP method journal October 1998
An SQP method for general nonlinear programs using only equality constrained subproblems journal August 1998
Valence correlation energies from pseudopotential calculations journal February 1996
Noncovalent Interactions by Quantum Monte Carlo journal April 2016
Soft pseudopotentials for efficient quantum Monte Carlo calculations: From Be to Ne and Al to Ar journal May 2001
Exact decoupling of the Dirac Hamiltonian. II. The generalized Douglas–Kroll–Hess transformation up to arbitrary order journal January 2004
Energy-consistent pseudopotentials for quantum Monte Carlo calculations journal June 2007
Binding Energies in Atomic Negative Ions: III journal November 1999
Core-valence partitioning and quasiparticle pseudopotentials journal August 1991
New generation of effective core potentials from correlated calculations: 2nd row elements dataset January 2018
Applications of quantum Monte Carlo methods in condensed systems text January 2010
Quantum Monte Carlo applied to solids text January 2013
Discovering correlated fermions using quantum Monte Carlo text January 2016
Separable Dual Space Gaussian Pseudo-potentials text January 1995
Molpro: a general-purpose quantum chemistry program package: Molpro
  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82
journal July 2011
Accuracy and limitations of the pseudopotential method: II. First-row molecules journal March 1977
Pseudopotential methods in condensed matter applications journal April 1989
Optimization algorithm for the generation of ONCV pseudopotentials journal November 2015
On the accuracy of averaged relativistic shape-consistent pseudopotentials journal October 1998
Relativistic Pseudopotentials: Their Development and Scope of Applications journal September 2011
Towards an exact description of electronic wavefunctions in real solids journal December 2012
Exact decoupling of the Dirac Hamiltonian. I. General theory journal August 2004
An analysis of core effects on shape-consistent pseudopotentials journal November 2004
Smooth relativistic Hartree–Fock pseudopotentials for H to Ba and Lu to Hg journal May 2005
Improved a b i n i t i o effective core potentials for molecular calculations journal December 1979
Treatment of intershell correlation effects in a b i n i t i o calculations by use of core polarization potentials. Method and application to alkali and alkaline earth atoms journal April 1984
Ground‐state properties of alkali dimers and their cations (including the elements Li, Na, and K) from a b i n i t i o calculations with effective core polarization potentials journal April 1984
Compact effective potentials and efficient shared‐exponent basis sets for the first‐ and second‐row atoms journal December 1984
Ab initio relativistic effective potentials with spin‐orbit operators. I. Li through Ar journal March 1985
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg journal January 1985
Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements journal January 1987
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
A b i n i t i o relativistic effective potentials with spin–orbit operators. IV. Cs through Rn journal November 1990
Generation of pseudopotentials from correlated wave functions journal June 1994
Norm-conserving pseudopotentials with chemical accuracy compared to all-electron calculations journal March 2013
Pseudopotentials for correlated electron systems journal July 2013
Correlated electron pseudopotentials for 3d-transition metals journal February 2015
Core-core and core-valence correlation energy atomic and molecular benchmarks for Li through Ar journal December 2015
Shape and energy consistent pseudopotentials for correlated electron systems journal May 2017
Magnitude of pseudopotential localization errors in fixed node diffusion quantum Monte Carlo journal June 2017
A new generation of effective core potentials for correlated calculations journal December 2017
Error Estimates for Solid-State Density-Functional Theory Predictions: An Overview by Means of the Ground-State Elemental Crystals journal October 2013
Applications of quantum Monte Carlo methods in condensed systems journal January 2011
Discovering correlated fermions using quantum Monte Carlo journal August 2016
Continuum variational and diffusion quantum Monte Carlo calculations journal December 2009
Benchmarking the pseudopotential and fixed-node approximations in diffusion Monte Carlo calculations of molecules and solids journal March 2016
Nonlinear ionic pseudopotentials in spin-density-functional calculations journal August 1982
Pseudopotentials that work: From H to Pu journal October 1982
Erratum: Pseudopotentials that work: From H to Pu journal February 1984
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism journal April 1990
Efficient pseudopotentials for plane-wave calculations journal January 1991
Many-body core-valence partitioning journal June 1993
Separable dual-space Gaussian pseudopotentials journal July 1996
All-electron and pseudopotential study of MgO: Equation of state, anharmonicity, and stability journal June 2003
Optimized norm-conserving Vanderbilt pseudopotentials journal August 2013
Quantum Monte Carlo applied to solids journal December 2013
Benchmarking the pseudopotential and fixed-node approximations in diffusion Monte Carlo calculations of molecules and solids journal March 2016
Norm-Conserving Pseudopotentials journal November 1979
Efficacious Form for Model Pseudopotentials journal May 1982
Ab initio Quantum Monte Carlo Calculations of Spin Superexchange in Cuprates: The Benchmarking Case of Ca 2 CuO 3 journal July 2014
Quantum Monte Carlo simulations of solids journal January 2001
Reproducibility in density functional theory calculations of solids journal March 2016
Improved ab initio effective core potentials for molecular calculations book December 1993
New generation of effective core potentials from correlated calculations: 2nd row elements dataset January 2018
Ab initio quantum Monte Carlo calculations of spin superexchange in cuprates: the benchmarking case of Ca$_2$CuO$_3$ text January 2014

Cited By (4)

A new generation of effective core potentials from correlated calculations: 3d transition metal series journal October 2018
A new generation of effective core potentials from correlated calculations: 4s and 4p main group elements and first row additions journal October 2019
Diffusion quantum Monte Carlo calculations with a recent generation of effective core potentials for ionization potentials and electron affinities journal December 2019
New generation of effective core potentials from correlated calculations: 3d transition metal series text January 2018

Similar Records

A new generation of effective core potentials from correlated calculations: 4s and 4p main group elements and first row additions
Journal Article · Tue Oct 08 20:00:00 EDT 2019 · Journal of Chemical Physics · OSTI ID:1595026

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS