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A new generation of effective core potentials for correlated calculations

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4995643· OSTI ID:1421640
 [1];  [1];  [2];  [2];  [3];  [2]
  1. North Carolina State Univ., Raleigh, NC (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. North Carolina State Univ., Raleigh, NC (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
+ Show Author Affiliations
Here, we outline ideas on desired properties for a new generation of effective core potentials (ECPs) that will allow valence-only calculations to reach the full potential offered by recent advances in many-body wave function methods. The key improvements include consistent use of correlated methods throughout ECP constructions and improved transferability as required for an accurate description of molecular systems over a range of geometries. The guiding principle is the isospectrality of all-electron and ECP Hamiltonians for a subset of valence states. We illustrate these concepts on a few first- and second-row atoms (B, C, N, O, S), and we obtain higher accuracy in transferability than previous constructions while using semi-local ECPs with a small number of parameters. In addition, the constructed ECPs enable many-body calculations of valence properties with higher (or same) accuracy than their all-electron counterparts with uncorrelated cores. This implies that the ECPs include also some of the impacts of core-core and core-valence correlations on valence properties. The results open further prospects for ECP improvements and refinements.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC04-94AL85000; NA0003525
OSTI ID:
1421640
Alternate ID(s):
OSTI ID: 1413026
Report Number(s):
SAND--2017-12940J; 659151
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 147; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (10)

Complementary first and second derivative methods for ansatz optimization in variational Monte Carlo journal January 2019
A new generation of effective core potentials from correlated calculations: 2nd row elements journal September 2018
A new generation of effective core potentials from correlated calculations: 3d transition metal series journal October 2018
A new scheme for fixed node diffusion quantum Monte Carlo with pseudopotentials: Improving reproducibility and reducing the trial-wave-function bias journal October 2019
A new generation of effective core potentials from correlated calculations: 4s and 4p main group elements and first row additions journal October 2019
The 2019 materials by design roadmap journal October 2018
QMCPACK : an open source ab initio quantum Monte Carlo package for the electronic structure of atoms, molecules and solids journal April 2018
Diffusion quantum Monte Carlo calculations with a recent generation of effective core potentials for ionization potentials and electron affinities journal December 2019
QMCPACK : An open source ab initio Quantum Monte Carlo package for the electronic structure of atoms, molecules, and solids text January 2018
New generation of effective core potentials from correlated calculations: 3d transition metal series text January 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY