화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.115, No.9, 1602-1608, 2011
Theoretical Investigations on Removal Reactions of Ethenol by H Atom
Ethenol is a recently identified combustion intermediate. However, its chemistry remains unclear. In present, work, the removal reactions of ethenol by H atom are investigated. The geometries of all species involved in the reaction are optimized at B3LYP/6-311++G(d,p), and their single point energies are extrapolated to the infinite-basis-set limit at the level CCSD(T). Energies are also calculated at G3B3, CBS-APNO, and CCSD(T)/6-311++G(3df, 2p) for comparison. A total of six elementary reactions, including four abstractions and two additions, with explicit transition states are investigated. The results show that the reactions are selective: for abstractions, the hydrogen atom, linked to the oxygen atom, is the most reactive; while for additions, the preferred carbon site is the head "CH2=". The rate constants are estimated in the temperature range 300-3000 K according to the conventional transition state theory with the Eckart tunneling model. The dominant channels are the two additions in the whole temperature range. The abstractions can be competitive at high temperature but still do not dominate. The calculated rate constants for the reverse reaction of (R6), syn-CH2=CHOH+H <-> CH3 center dot CHOH, are consistent with the available literature values. Finally, the Fukui functions are calculated to analyze the site reactivity.