skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on September 14, 2019

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

Abstract

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 typicalmore » discrepancies of ≈ 0.01 eV or smaller.« less

Authors:
 [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)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1441470
Alternate Identifier(s):
OSTI ID: 1470794
Report Number(s):
SAND-2018-4735J
Journal ID: ISSN 0021-9606; 662779; TRN: US1900963
Grant/Contract Number:  
AC04-94AL85000; NA0003525
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 10; 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; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Bennett, Michael Chandler, Melton, Cody A., Annaberdiyev, Abdulgani, Wang, Guangming, Shulenburger, Luke, and Mitas, Lubos. New generation of effective core potentials from correlated calculations: 2nd row elements. United States: N. p., 2018. Web. doi:10.1063/1.5038135.
Bennett, Michael Chandler, Melton, Cody A., Annaberdiyev, Abdulgani, Wang, Guangming, Shulenburger, Luke, & Mitas, Lubos. New generation of effective core potentials from correlated calculations: 2nd row elements. United States. doi:10.1063/1.5038135.
Bennett, Michael Chandler, Melton, Cody A., Annaberdiyev, Abdulgani, Wang, Guangming, Shulenburger, Luke, and Mitas, Lubos. Fri . "New generation of effective core potentials from correlated calculations: 2nd row elements". United States. doi:10.1063/1.5038135.
@article{osti_1441470,
title = {New generation of effective core potentials from correlated calculations: 2nd row elements},
author = {Bennett, Michael Chandler and Melton, Cody A. and Annaberdiyev, Abdulgani and Wang, Guangming and Shulenburger, Luke and Mitas, Lubos},
abstractNote = {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.},
doi = {10.1063/1.5038135},
journal = {Journal of Chemical Physics},
number = 10,
volume = 149,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on September 14, 2019
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Ab initio relativistic effective potentials with spin?orbit operators. I. Li through Ar
journal, March 1985

  • Fernandez Pacios, Luis; Christiansen, P. A.
  • The Journal of Chemical Physics, Vol. 82, Issue 6, p. 2664-2671
  • DOI: 10.1063/1.448263