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Effect of two-electron spin-orbit interactions on singlet-triplet transition probabilities†

 

作者: JackL. Ginsburg,   Lionel Goodman,  

 

期刊: Molecular Physics  (Taylor Available online 1968)
卷期: Volume 15, issue 5  

页码: 441-451

 

ISSN:0026-8976

 

年代: 1968

 

DOI:10.1080/00268976800101341

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Previously reported calculations concerned with spin-orbit enhancement of molecularS-Ttransitions have utilized an approximate one-electron spin-orbit Hamiltonian. The approximations are carried over from atomic spin-orbit theory and are justified on the basis of physical reasoning strictly applicable only to diagonal matrix elements. In order to test critically these assumptions, a treatment of spin-orbit enhancement of the formaldehyde3A2↔1A1transition is given using the complete spin-orbit Hamiltonian. A one-electron approximation to the spin-orbit Hamiltonian is found to be conceptually valid. The one-electron approximation which most closely approximates the complete spin-orbit Hamiltonian is the bare nuclear field Hamiltonian. Calculations on the lowest triplet state of the azines yield similar results.

 

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