Experimental and Computational Studies of the Phenyl Radical Reaction with Allene

Autor:	I. V. Tokmakov, Ming-Chang Lin, J. Park
Rok vydání:	2007
Předmět:	Arrhenius equation Chemistry Allene Radical Kinetics Branching (polymer chemistry) Kinetic energy Mass spectrometry symbols.namesake chemistry.chemical_compound Reaction rate constant Computational chemistry symbols Physical chemistry Physical and Theoretical Chemistry
Zdroj:	The Journal of Physical Chemistry A. 111:6881-6889
ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp0708502
Popis:	The kinetics for the gas-phase reaction of phenyl radicals with allene has been measured by cavity ring-down spectrometry (CRDS), and the mechanism and initial product branching have been elucidated with the help of quantum-chemical calculations. The absolute rate constant measured by the CRDS technique can be expressed by the following Arrhenius equation: kallene (T=301-421 K)=(4.07+/-0.38)x10(11) exp[-(1865+/-85)/T] cm3 mol(-1) s(-1). Theoretical calculations, employing high level G2M energetic and IRCMax(RCCSD(T)//B3LYP-DFT) molecular parameters, indicate that under our experimental conditions the most preferable reaction channel is the addition of phenyl radicals to the terminal carbon atoms in allene. Predicted total rate constants agree with the experimental values within 40%. Calculated total and branching rate constants are provided for high-T kinetic modeling.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::f4f778e94637ff71fed9e059138edd57 https://doi.org/10.1021/jp0708502 Zobrazit plný text záznamu