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Title: Toward the evaluation of intersystem crossing rates with variational relativistic methods

Abstract

The change in electronic state from one spin multiplicity to another, known as intersystem crossing, occurs in molecules via the relativistic phenomenon of spin-orbit coupling. Current means of estimating intersystem crossing rates rely on the perturbative evaluation of spin-orbit coupling effects. This perturbative approach, valid in lighter atoms where spin-orbit coupling is weaker, is expected to break down for heavier elements where relativistic effects become dominant. Methods which incorporate spin-orbit effects variationally, such as the exact-two-component (X2C) method, will be necessary to treat this strong-coupling regime. In this paper, we present a novel procedure which produces a diabatic basis of spin-pure electronic states coupled by spin-orbit terms, generated from fully variational relativistic calculations. This method is implemented within X2C using time-dependent density-functional theory and is compared to results from a perturbative relativistic study in the weak spin-orbit coupling regime. Additional calculations on a more strongly spin-orbit-coupled [UO2Cl4]2- complex further illustrate the strengths of this method. This procedure will be valuable in the estimation of intersystem crossing rates within strongly spin-coupled species.

Authors:
ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1610904
Alternate Identifier(s):
OSTI ID: 1559099
Grant/Contract Number:  
SC0006863; AC02-06CH11357; CHE-1856210; MRI-1624430
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; Chemistry; Physics

Citation Formats

Valentine, Andrew J. S., and Li, Xiaosong. Toward the evaluation of intersystem crossing rates with variational relativistic methods. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5113815.
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Valentine, Andrew J. S., & Li, Xiaosong. Toward the evaluation of intersystem crossing rates with variational relativistic methods. United States. https://doi.org/10.1063/1.5113815
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Valentine, Andrew J. S., and Li, Xiaosong. Wed . "Toward the evaluation of intersystem crossing rates with variational relativistic methods". United States. https://doi.org/10.1063/1.5113815. https://www.osti.gov/servlets/purl/1610904.
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@article{osti_1610904,
title = {Toward the evaluation of intersystem crossing rates with variational relativistic methods},
author = {Valentine, Andrew J. S. and Li, Xiaosong},
abstractNote = {The change in electronic state from one spin multiplicity to another, known as intersystem crossing, occurs in molecules via the relativistic phenomenon of spin-orbit coupling. Current means of estimating intersystem crossing rates rely on the perturbative evaluation of spin-orbit coupling effects. This perturbative approach, valid in lighter atoms where spin-orbit coupling is weaker, is expected to break down for heavier elements where relativistic effects become dominant. Methods which incorporate spin-orbit effects variationally, such as the exact-two-component (X2C) method, will be necessary to treat this strong-coupling regime. In this paper, we present a novel procedure which produces a diabatic basis of spin-pure electronic states coupled by spin-orbit terms, generated from fully variational relativistic calculations. This method is implemented within X2C using time-dependent density-functional theory and is compared to results from a perturbative relativistic study in the weak spin-orbit coupling regime. Additional calculations on a more strongly spin-orbit-coupled [UO2Cl4]2- complex further illustrate the strengths of this method. This procedure will be valuable in the estimation of intersystem crossing rates within strongly spin-coupled species.},
doi = {10.1063/1.5113815},
journal = {Journal of Chemical Physics},
number = 8,
volume = 151,
place = {United States},
year = {2019},
month = {8}
}
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