Ud. Priyakumar et Gn. Sastry, Structure, stability and reactivity parameters of (CH)(8) isomers and their cation and anion radical counterparts: A theoretical study, I J CHEM A, 39(1-3), 2000, pp. 92-99
Citations number
30
Categorie Soggetti
Chemistry
Journal title
INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY
Among the hydrocarbons with (CH)(2k) (k = 1, 2, 3, 4,...) structural formul
a, (CH)(8) where k = 4, possesses nineteen local minima at semiempirical le
vel with comparable heats of formation. AM1 procedure is found to be better
than MNDO and PM3 in evaluating the heats of formation and geometries base
d on comparison with available experimental data of the neutral isomers. Ve
rtical and adiabatic electron affinities and ionization potentials have bee
n calculated for all the available isomers. The relative energy ordering is
mainly controlled by the electronic factors rather than the strain. Koopma
n's theorem is not expected to yield reliable answers for ionization potent
ials, as the orbital relaxation seems to be very high for some isomers. The
major geometric distortions are due to either Jahn-Teller distortions or s
trong vibronic interactions and the consequent reordering of the skeleton.
Relaxation energies from vertical to adiabatic states are roughly proportio
nal to the geometric deformations that occur upon ionization or addition of
an electron.