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V. N. Belevskii
Ionic processes in
radiation chemistry of oxygen-containing compound in condensed phase
Abstract
The mechanisms of
ion-radical processes induced by X-rays and
-radiolysis in different organic compaund (alcohols, ethers, linear and
cyclic ethers, acetales and diethers, aldehydes, ketones, carbonic acids and
amides) have been investigated in the radiation chemical laboratory, department
of chemistry, Moscow State University. Structure and reactivity of radical
cations of same organic compounds in irradiated frozen freonic matrix were
studied by ESR technique. The radical products resulted from radiolysis in neat
organic substunces at liquid phase were studied using spin trapping techique.
Electronic, spin and energy characteristics of radical cations of series of
alcohols, amides, aldehydes, linear and cyclic ethers and acetales were
calculated quantum chemically using MNDO-UHF, DFT (PBE) and ab initio MP2
methods. The resalts of calculations are effectivily correlated with ESR data
obtained in freonic metrices and in liquid phase. The analysis of this
characteristics and ESR data allowed to predict the most probable mechanisms of
intermediats transformation. Electronic structure and geometry are controled
the thermal and photochemical transformation of radical cations: ion-molecular
reactins, isomerization, rearrangements and fragmentations.
Copyright (C) Chemistry Dept., Moscow State University, 2002
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