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This content will become publicly available on December 12, 2018

Title: A new generation of effective core potentials for correlated calculations

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.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [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)
Publication Date:
Report Number(s):
SAND-2017-12940J; SAND-2018-4735J
Journal ID: ISSN 0021-9606; 659151; TRN: US1801536
Grant/Contract Number:
AC04-94AL85000; N. 4000144475; NA0003525
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
OSTI Identifier:
1421640
Alternate Identifier(s):
OSTI ID: 1413026; OSTI ID: 1441470