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Title: Implementation and Validation of Fully Relativistic GW Calculations: Spin–Orbit Coupling in Molecules, Nanocrystals, and Solids

Abstract

We present an implementation of G0W0 calculations including spin–orbit coupling (SOC) enabling investigations of large systems, with thousands of electrons, and we discuss results for molecules, solids, and nanocrystals. Using a newly developed set of molecules with heavy elements (called GW-SOC81), we find that, when based upon hybrid density functional calculations, fully relativistic (FR) and scalar-relativistic (SR) G0W0 calculations of vertical ionization potentials both yield excellent performance compared to experiment, with errors below 1.9%. We demonstrate that while SR calculations have higher random errors, FR calculations systematically underestimate the VIP by 0.1 to 0.2 eV. We further verify that SOC effects may be well approximated at the FR density functional level and then added to SR G0W0 results for a broad class of systems. We also address the use of different root-finding algorithms for the G0W0 quasiparticle equation and the significant influence of including d electrons in the valence partition of the pseudopotential for G0W0 calculations. Lastly, we present statistical analyses of our data, highlighting the importance of separating definitive improvements from those that may occur by chance due to a limited number of samples. We suggest the statistical analyses used here will be useful in the assessment of themore » accuracy of a large variety of electronic structure methods« less

Authors:
 [1];  [2];  [3];  [2]
  1. Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637, United States
  2. Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637, United States, Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
  3. International Center for Materials Nanoarchitectonics, Global Research Center for Environment and Energy based on Nanomaterials Science, and Center for Materials Research by Information Integration, National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044, Japan
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1262100
Alternate Identifier(s):
OSTI ID: 1326817
Grant/Contract Number:  
5J-30161-0010A; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Name: Journal of Chemical Theory and Computation Journal Volume: 12 Journal Issue: 8; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Scherpelz, Peter, Govoni, Marco, Hamada, Ikutaro, and Galli, Giulia. Implementation and Validation of Fully Relativistic GW Calculations: Spin–Orbit Coupling in Molecules, Nanocrystals, and Solids. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.jctc.6b00114.
Scherpelz, Peter, Govoni, Marco, Hamada, Ikutaro, & Galli, Giulia. Implementation and Validation of Fully Relativistic GW Calculations: Spin–Orbit Coupling in Molecules, Nanocrystals, and Solids. United States. https://doi.org/10.1021/acs.jctc.6b00114
Scherpelz, Peter, Govoni, Marco, Hamada, Ikutaro, and Galli, Giulia. Wed . "Implementation and Validation of Fully Relativistic GW Calculations: Spin–Orbit Coupling in Molecules, Nanocrystals, and Solids". United States. https://doi.org/10.1021/acs.jctc.6b00114.
@article{osti_1262100,
title = {Implementation and Validation of Fully Relativistic GW Calculations: Spin–Orbit Coupling in Molecules, Nanocrystals, and Solids},
author = {Scherpelz, Peter and Govoni, Marco and Hamada, Ikutaro and Galli, Giulia},
abstractNote = {We present an implementation of G0W0 calculations including spin–orbit coupling (SOC) enabling investigations of large systems, with thousands of electrons, and we discuss results for molecules, solids, and nanocrystals. Using a newly developed set of molecules with heavy elements (called GW-SOC81), we find that, when based upon hybrid density functional calculations, fully relativistic (FR) and scalar-relativistic (SR) G0W0 calculations of vertical ionization potentials both yield excellent performance compared to experiment, with errors below 1.9%. We demonstrate that while SR calculations have higher random errors, FR calculations systematically underestimate the VIP by 0.1 to 0.2 eV. We further verify that SOC effects may be well approximated at the FR density functional level and then added to SR G0W0 results for a broad class of systems. We also address the use of different root-finding algorithms for the G0W0 quasiparticle equation and the significant influence of including d electrons in the valence partition of the pseudopotential for G0W0 calculations. Lastly, we present statistical analyses of our data, highlighting the importance of separating definitive improvements from those that may occur by chance due to a limited number of samples. We suggest the statistical analyses used here will be useful in the assessment of the accuracy of a large variety of electronic structure methods},
doi = {10.1021/acs.jctc.6b00114},
journal = {Journal of Chemical Theory and Computation},
number = 8,
volume = 12,
place = {United States},
year = {2016},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jctc.6b00114

Citation Metrics:
Cited by: 12 works
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