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Title: Spin–Orbit Coupling via Four-Component Multireference Methods: Benchmarking on p-Block Elements and Tentative Recommendations

Abstract

Within current electronic structure theory methods, fully relativistic four-component (4c) approaches based on the Dirac Hamiltonian treat spin–orbit coupling with the most rigor. The spin treatment arises naturally from the formulation and does not need to be included ad hoc. Spin–orbit splittings can provide insightful benchmark criteria for the assessment of 4c methods; however, there have not been extensive studies in this respect. Spin–orbit splittings of the p-block elements B–I were computed using the 4c-CASSCF, 4c-CASPT2, and 4c-MR-CISD+Q methods, as recently implemented in BAGEL, with uncontracted Dunning basis sets. Comparison with experiment reveals that the four-component methods yield good results, with most of the computed splittings falling within 15% of the experimental values. A large basis set is needed to obtain accurate splittings of the light elements B–F, while splittings of heavier elements show little basis dependence. The 4c-MR-CISD+Q method gave the best splittings for light elements, while 4c-CASSCF showed the best splittings for elements beyond fluorine. In conclusion, the 4c-CASPT2 method gave the best splittings for group 13 atoms.

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Univ. of Georgia, Athens, GA (United States)
  2. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1468299
Grant/Contract Number:  
SC0018412
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 14; Journal Issue: 3; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Boyi, Vandezande, Jonathon E., Reynolds, Ryan D., and Schaefer, III, Henry F. Spin–Orbit Coupling via Four-Component Multireference Methods: Benchmarking on p-Block Elements and Tentative Recommendations. United States: N. p., 2018. Web. doi:10.1021/acs.jctc.7b00989.
Zhang, Boyi, Vandezande, Jonathon E., Reynolds, Ryan D., & Schaefer, III, Henry F. Spin–Orbit Coupling via Four-Component Multireference Methods: Benchmarking on p-Block Elements and Tentative Recommendations. United States. doi:10.1021/acs.jctc.7b00989.
Zhang, Boyi, Vandezande, Jonathon E., Reynolds, Ryan D., and Schaefer, III, Henry F. Tue . "Spin–Orbit Coupling via Four-Component Multireference Methods: Benchmarking on p-Block Elements and Tentative Recommendations". United States. doi:10.1021/acs.jctc.7b00989. https://www.osti.gov/servlets/purl/1468299.
@article{osti_1468299,
title = {Spin–Orbit Coupling via Four-Component Multireference Methods: Benchmarking on p-Block Elements and Tentative Recommendations},
author = {Zhang, Boyi and Vandezande, Jonathon E. and Reynolds, Ryan D. and Schaefer, III, Henry F.},
abstractNote = {Within current electronic structure theory methods, fully relativistic four-component (4c) approaches based on the Dirac Hamiltonian treat spin–orbit coupling with the most rigor. The spin treatment arises naturally from the formulation and does not need to be included ad hoc. Spin–orbit splittings can provide insightful benchmark criteria for the assessment of 4c methods; however, there have not been extensive studies in this respect. Spin–orbit splittings of the p-block elements B–I were computed using the 4c-CASSCF, 4c-CASPT2, and 4c-MR-CISD+Q methods, as recently implemented in BAGEL, with uncontracted Dunning basis sets. Comparison with experiment reveals that the four-component methods yield good results, with most of the computed splittings falling within 15% of the experimental values. A large basis set is needed to obtain accurate splittings of the light elements B–F, while splittings of heavier elements show little basis dependence. The 4c-MR-CISD+Q method gave the best splittings for light elements, while 4c-CASSCF showed the best splittings for elements beyond fluorine. In conclusion, the 4c-CASPT2 method gave the best splittings for group 13 atoms.},
doi = {10.1021/acs.jctc.7b00989},
journal = {Journal of Chemical Theory and Computation},
number = 3,
volume = 14,
place = {United States},
year = {2018},
month = {2}
}

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