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Toward the evaluation of intersystem crossing rates with variational relativistic methods.
- Source :
-
Journal of Chemical Physics . 8/28/2019, Vol. 151 Issue 8, pN.PAG-N.PAG. 10p. 3 Diagrams, 4 Charts. - Publication Year :
- 2019
-
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. 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 [ U O 2 C l 4 ] 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. [ABSTRACT FROM AUTHOR]
- Subjects :
- *HEAVY elements
*RATES
*SPIN-orbit interactions
Subjects
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 151
- Issue :
- 8
- Database :
- Academic Search Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 138370783
- Full Text :
- https://doi.org/10.1063/1.5113815