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Title: A new generation of effective core potentials from correlated calculations: 3d transition metal series

Abstract

Recently, we have introduced a new generation of effective core potentials (ECPs) designed for accurate correlated calculations but equally useful for a broad variety of approaches. The guiding principle has been the isospectrality of all-electron and ECP Hamiltonians for a subset of valence many-body states using correlated, nearly-exact calculations. We present such ECPs for the 3d transition series Sc to Zn with Ne-core, i.e., with semi-core 3s and 3p electrons in the valence space. Besides genuine many-body accuracy, the operators are simple, being represented by a few gaussians per symmetry channel with resulting potentials that are bounded everywhere. The transferability is checked on selected molecular systems over a range of geometries. The ECPs show a high overall accuracy with valence spectral discrepancies typically ≈0.01-0.02 eV or better. Finally, they also reproduce binding curves of hydride and oxide molecules typically within 0.02-0.03 eV deviations over the full non-dissociation range of interatomic distances.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3];  [1]
  1. North Carolina State Univ., Raleigh, NC (United States). Dept. of Physics
  2. North Carolina State Univ., Raleigh, NC (United States). Dept. of Physics; Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); North Carolina State Univ., Raleigh, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1477870
Alternate Identifier(s):
OSTI ID: 1475478
Report Number(s):
SAND-2018-5251J
Journal ID: ISSN 0021-9606; 663180
Grant/Contract Number:  
NA0003525
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; effective core potentials; oxides; correlation energy; molecular properties; transition metals

Citation Formats

Annaberdiyev, Abdulgani, Wang, Guangming, Melton, Cody A., Chandler Bennett, M., Shulenburger, Luke, and Mitas, Lubos. A new generation of effective core potentials from correlated calculations: 3d transition metal series. United States: N. p., 2018. Web. doi:10.1063/1.5040472.
Annaberdiyev, Abdulgani, Wang, Guangming, Melton, Cody A., Chandler Bennett, M., Shulenburger, Luke, & Mitas, Lubos. A new generation of effective core potentials from correlated calculations: 3d transition metal series. United States. doi:10.1063/1.5040472.
Annaberdiyev, Abdulgani, Wang, Guangming, Melton, Cody A., Chandler Bennett, M., Shulenburger, Luke, and Mitas, Lubos. Wed . "A new generation of effective core potentials from correlated calculations: 3d transition metal series". United States. doi:10.1063/1.5040472. https://www.osti.gov/servlets/purl/1477870.
@article{osti_1477870,
title = {A new generation of effective core potentials from correlated calculations: 3d transition metal series},
author = {Annaberdiyev, Abdulgani and Wang, Guangming and Melton, Cody A. and Chandler Bennett, M. and Shulenburger, Luke and Mitas, Lubos},
abstractNote = {Recently, we have introduced a new generation of effective core potentials (ECPs) designed for accurate correlated calculations but equally useful for a broad variety of approaches. The guiding principle has been the isospectrality of all-electron and ECP Hamiltonians for a subset of valence many-body states using correlated, nearly-exact calculations. We present such ECPs for the 3d transition series Sc to Zn with Ne-core, i.e., with semi-core 3s and 3p electrons in the valence space. Besides genuine many-body accuracy, the operators are simple, being represented by a few gaussians per symmetry channel with resulting potentials that are bounded everywhere. The transferability is checked on selected molecular systems over a range of geometries. The ECPs show a high overall accuracy with valence spectral discrepancies typically ≈0.01-0.02 eV or better. Finally, they also reproduce binding curves of hydride and oxide molecules typically within 0.02-0.03 eV deviations over the full non-dissociation range of interatomic distances.},
doi = {10.1063/1.5040472},
journal = {Journal of Chemical Physics},
number = 13,
volume = 149,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

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Cited by: 3 works
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Figures / Tables:

FIG. 1 FIG. 1: Spread of the contributions to the excitation energy for a variety of ECPs compared to all-electron for the Fe atom. ΔHF shows the variation in the HF errors, whereas ΔcVV shows the variation in the correlation energy error compared against the AE valence-valence correlation energy.

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