Affiliation:
1. Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University, 930 Sakaedani, Wakayama 640-8510, Japan
Abstract
Nuclear couplings for the Se-Se bonds,J1(Se, Se), are analyzed on the basis of the molecular orbital (MO) theory. The values are calculated by employing the tripleζbasis sets of the Slater type at the DFT level.J1(Se, Se)are calculated modeled by MeSeSeMe (1a), which shows the typical torsional angular dependence onϕ(CMeSeSeCMe). The dependence explains well the observedJ1(Se, Se)obsdof small values (≤64 Hz) forRSeSeR′(1) (simple derivatives of1a) and large values (330–380 Hz) observed for 4-substituted naphto[1,8-c,d]-1,2-diselenoles (2) which correspond tosymperiplanardiselenides.J1(Se, Se :2) becomes larger as the electron density on Se increases. The paramagnetic spin-orbit terms contribute predominantly. The contributions are evaluated separately from each MO(ψi)and eachψi→ψatransition, whereψiandψaare occupied and unoccupied MO's, respectively. The separate evaluation enables us to recognize and visualize the origin and the mechanism of the couplings.
Funder
Ministry of Education, Culture, Sports, Science, and Technology
Subject
Inorganic Chemistry,Organic Chemistry,Biochemistry
Cited by
8 articles.
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