Spin-orbit coupling in the intersystem crossing of the ring-opened oxirane biradical
- Univ. of Uppsala (Sweden)
- Cherkassy Engineering and Technological Institute (Ukraine)
- Univ. of Linkoeping (Sweden)
The intersystem crossing (ISC) between the lowest triplet and singlet states occurring in the reaction of atomic oxygen with ethylene was studied. The importance of spin-orbit coupling (SOC) in oxirane biradicals (CR{prime}R{double_prime}-CRR*-O) is stressed through calculations where the spin-orbit matrix elements over the full Breit-Pauli SOC operator has been obtained in the singlet-triplet crossing region. The calculations are performed with a multiconfigurational linear response approach, in which the spin-orbit couplings are obtained from triplet response functions using differently correlated singlet-reference-state wave functions. Computational results confirm earlier semiempirical predictions of the spin-orbit coupling as an important mechanism behind the ring opening of oxiranes and addition of oxygen O({sup 3}P) atoms to alkenes. 32 refs., 2 figs., 5 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 459109
- Journal Information:
- International Journal of Quantum Chemistry, Journal Name: International Journal of Quantum Chemistry Journal Issue: 1 Vol. 55; ISSN IJQCB2; ISSN 0020-7608
- Country of Publication:
- United States
- Language:
- English
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