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Conformation Analysis in Light of Localization and Delocalization

Peter R. Surjan ; CHINOIN Pharmaceutical and Chemical Works, H-1325 Budapest P.O.B. 110., Hungary


Puni tekst: engleski pdf 8.611 Kb

str. 289-295

preuzimanja: 276

citiraj


Sažetak

The role of electron delocalization in conformational effects,
especially in giving rise to barrier forces is discussed in the bond
orbital framework. Using orthogonal bond orbitals, the effects of
through space and through bond delocalization interactions is demonstrated;numerical examples show the predominant role of
through space delocalization. The total energy obtained by strictly
localized orthogonal bond orbitals is shown to be rather independent
of the relative orientations of the bonds. Second order perturbative
delocalization energy corrections are interpreted as bond-
bond pair potentials within the orthogonal basis. On the contrary,
nonorthogonal bond orbitals lead to an energy expression which
is very sensitive to the bond orientations even if one neglects completelyelectron delocalization. The origin of the barriers is discussed
in terms of nonempirical bond-bond pair potentials.

Ključne riječi

Hrčak ID:

194234

URI

https://hrcak.srce.hr/194234

Datum izdavanja:

30.6.1983.

Posjeta: 737 *