Probing weak molecular orbital interactions in non-conjugated diene molecules by means of near-edge X-ray absorption spectroscopy

Felicissimo, V.C.KTH,Teoretisk kemi,Universidade Federal de Minas Gerais, Brazil (författare)

QC 20101022 Tidigare titel: Probing through-bond and through-space interactions by means of near-edge x-ray absorption spectroscopy. A theoretical study on non-conjugated diene molecules.
Carbon and oxygen near-edge X-ray absorption fine structure (NEXAFS) spectra of 1,4-cyclohexadiene, p-benzoquinone, norbornadiene, norbornadienone, and cis-cis-[4,4,2]propella-3,8-diene-11,12-dione were calculated by means of Hartree-Fock and hybrid density functional theory using the static-exchange (STEX) approximation. The NEXAFS spectra are used as a probe to identify weak molecular interactions between the two non-conjugated ethylenic pi* orbitals present in these molecules. We show that the X-ray absorption spectrum of 1,4-cyclohexadiene exhibits some particular spectral structures in the discrete energy region that evidence diene through-bond orbital interaction, whereas absorption peaks are identified in the norbornadiene and norbornadienone spectra that indicate effective through-space orbital interactions. The molecular structure of the cis-cis-[4,4,2]propella-3,8-diene-11,12-dione isomer is such that the indirect through-bond or through-space diene orbital interactions are too weak to be assigned by its C1s NEXAFS spectrum.

Ingår i:Journal of Physical Chemistry A: American Chemical Society (ACS)109:33, s. 7385-73951089-56391520-5215

Av författaren/redakt...: Felicissimo, V.C ...; Cesar, A.; Luo, Yi; Gel'mukhanov, Fa ...; Ågren, Hans

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