Naslov
Nature of the Highest Occuppied Molecular Orbitals of trans- and cis-Bicyclo[4.1.0]hept-3-enes

Autori
Gassman, Paul G. ; Mlinarić-Majerski, Kata ; Kovač, Branka ; Chen, Han ; Dixon, David A.

Izvornik
Journal of physical organic chemistry (0894-3230) 8 (1995), 3; 149-158

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
trans-bicyclo{;; 4.1.0};; hept-3-enes; cis-bicyclo{;; 4.1.0};; hept-3-enes; `twist`bent sigma bond; photoelectron spectroscopic studies

Sažetak
Photoelectron spectra of trans-bicyclo{; ; 4.1.0}; ; hept-3-ene and two methyl derivatives, 1-3, and cis-bicyclo{; ; 4.1.0}; ; hept-3-ene and three of its derivatives, 4-7, were measured. Ab initio molecular orbital (MO) and density functional theory (DFT) calculations were performed on these compounds. By combining the results of the experimental computational trends, it was established that the highest occupied molecular orbitals (HOMOs) of 1-3 are the `twist`bent sigma bond at the fusion between the two rings whereas for 4-7 the HOMOs are the pi orbital in the six-membered ring. The DFT ordering is the same as the suggested by the photoelectron spectra whereas at the MO level the HOMO always coresponds to the pi orbital. The intensities of the photoelectron spectra were calculated at the DFT level and good qualitative agreement with experiment was found.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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