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Rate coefficients and branching ratios for unimolecular reactions of alkoxyl radicals in the temperature range 200 to 1500 K and in the pressure range 10 −2  to 10 4  bar are presented. Special emphasis is given to the change of the relative importance of different reaction channels. This is evident for longer chain alkoxyl radicals which at lower temperatures undergo isomerisation  via  an energetically favourable six-member ring transition state. At temperatures above &gt;600 K, however, the rates of the alternative decomposition pathways become faster than that of isomerisation.

zeitschrift für physikalische chemie

Kinetics and Dynamics of Multi-Channel Unimolecular Reactions of Alkoxyl Radicals Over an Extended Range of Temperature and Pressure. A Combined Quantum Chemical/RRKM Dynamical Study