Probing weak molecular orbital interactions in non-conjugated diene molecules by means of near-edge X-ray absorption spectroscopy
2005 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 109, no 33, 7385-7395 p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2005. Vol. 109, no 33, 7385-7395 p.
through-bond interactions, negative-ion states, photoelectron-spectroscopy, electron transmission, para-benzoquinone, shell excitation, anion states, pi-orbitals, spectra, 1, 4-cyclohexadiene
IdentifiersURN: urn:nbn:se:kth:diva-14990DOI: 10.1021/jp044757eISI: 000231425900007ScopusID: 2-s2.0-24944579925OAI: oai:DiVA.org:kth-14990DiVA: diva2:333031
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.2010-08-052010-08-052016-09-02Bibliographically approved