ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The electronic structure of the C2nH2n+2 trans-polyenes, n = 3-7, is calculated by the Discrete Variational Xα method (DVM-Xα). The valence ionization potentials (IP) calculated using the Clementi double zeta basis agree with the known experimental data within several tenths an electron volt. However, the DVM energies of the π → π* optical excitations are systematically underestimated by 0.8-1.0 eV. For polyenes with equal C - C bond lengths, the computed energies of the first optical transitions are smaller than those of polyenes with alternating C - C bond lengths. The charge distribution in polyenes is analyzed in the framework of a Mulliken scheme. The composition of the frontier molecular orbitals (MO) is analyzed.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560300508
