0000000000677006
AUTHOR
P. M. Viruela‐martin
Electronic structure of tetraphenyldithiapyranylidene : A valence effective Hamiltonian theoretical investigation
We present a theoretical investigation of the electronic structure of tetraphenyldithiapyranylidene (DIPSΦ4) using the nonempirical valence effective Hamiltonian (VEH) method. Molecular geometries are optimized at the semiempirical PM3 level which predicts an alternating nonaromatic structure for the dithiapyranylidene (DIPS) framework. The VEH one‐electron energy level distribution calculated for DIPSΦ4 is presented as a theoretical XPS simulation and is analyzed by comparison to the electronic structure of its molecular components DIPS and benzene. The theoretical VEH spectrum is found to be fully consistent with the experimental solid‐state x‐ray photoelectron spectroscopy (XPS) spectrum…
Valence electronic structure of C60: Theoretical analysis of photoemission data
Abstract We present a theoretical investigation of the valence band photoemission spectra of C 60 using the nonempirical valence effective Hamiltonian (VEH) method. The VEH-DOVS curves calculated for the C 60 molecule are found to be in excellent agreement with synchrotron-radiation photoemission spectra reported for C 60 films. A detailed interpretation of all the photoemission bands is performed in the light of the VEH results.
Theoretical determination of the geometric and electronic structures of oligorylenes and poli(peri‐naphthalene)
We present a theoretical investigation of the electronic structure of oligorylenes (from perylene to heptarylene, including also the naphthalene molecule) and their corresponding polymer poly(peri‐naphthalene) (PPN) using the nonempirical valence effective (VEH) method. The geometry of the unit cell used to generate the polymer is extrapolated from the PM3‐optimized molecular geometries of the longest oligorylenes. That geometry shows some bond alternation along the perimeter carbon chains and a bond length of ≊1.46 Å is calculated for the peri bonds connecting the naphthalene units. The VEH one‐electron energy level distributions calculated for oligorylenes are used to interpret the experi…
Geometric and electronic structure of dithiapyranylidine: evolution upon oxidation
Abstract We present a theoretical investigation of the modifications that successive oxidation induces on the geometric and electronic structures of the π-electron donor dithiapyranylidene. The lengthening of the double bonds and the shortening of the single bonds calculated as the molecular charge increases indicate a gain of aromaticity with oxidation. Both the geometricand the electronic structure of dithiapyranylidene show a clear evolution towards those of biphenyl as oxidation takes place.