Roaming Radicals in the Thermal Decomposition of Dimethyl Ether: Experiment and Theory
The thermal dissociation of dimethyl ether has been studied with a combination of reflected shock tube experiments and ab initio dynamics simulations coupled with transition state theory based master equation calculations. The experiments use the extraordinary sensitivity provided by H-atom ARAS detection with an unreversed light source to measure both the total decomposition rate and the branching to radical products versus molecular products, with the molecular products arising predominantly through roaming according to the theoretical analysis. The experimental observations also provide a measure of the rate coefficient for H+CH3OCH3. An evaluation of the available experimental results for H+CH3OCH3 can be expressed by a three parameter Arrhenius expression as, k=6.54×10-24T4.13exp(-896/T)cm3molecule-1s-1(273-1465K)The potential energy surface is explored with high level ab initio electronic structure theory. The dynamics of roaming versus radical formation is studied with a reduced dimensional trajectory approach. The requisite potential energy surface is obtained from an interpolative moving least squares fit to wide-ranging ab initio data for the long-range interactions between methyl and methoxy. The predicted roaming and radical micro-canonical fluxes are incorporated in a master equation treatment of the temperature and pressure dependence of the dissociation process. The tight (i.e., non-roaming) transition states leading to a variety of additional molecular fragments are also included in the master equation analysis, but are predicted to have a negligible contribution to product formation. The final theoretical results reliably reproduce the measured dissociation rate to radical products reported here and are well reproduced over the 500-2000. K temperature range and the 0.01-300. bar pressure range by the following modified Arrhenius parameters for the Troe falloff format:. k1,∞(T)=2.33×1019T-0.661exp(-42345/T)s-1k1,0(T)=2.86×1035T-11.4exp(-46953/T)cm3molecule-1s-1Fcent(T)=exp(-T/880)The experimentally observed branching ratio of 0.19 ± 0.07 provides a direct measure of the contribution from the roaming radical mechanism. The theoretical analysis predicts a much smaller roaming contribution of 0.02.
R. S. Sivaramkrishnan et al., "Roaming Radicals in the Thermal Decomposition of Dimethyl Ether: Experiment and Theory," Combustion and Flame, vol. 158, no. 4, pp. 618-632, Elsevier, Apr 2011.
The definitive version is available at https://doi.org/10.1016/j.combustflame.2010.12.017
United States. Department of Energy
Keywords and Phrases
Ab initio; Ab initio dynamics; Abstraction; Arrhenius expressions; Arrhenius parameters; Branching ratio; Decomposition rate; Dimethyl ethers; Direct measures; Dissociation process; Dissociation rates; Electronic structure theory; Experimental observation; Long range interactions; Master equations; Methoxy; Molecular fragments; Moving least squares; Pressure dependence; Pressure ranges; Product formation; Radical formation; Radical mechanism; Rate coefficients; Reduced-dimensional; Reflected shocks; Temperature range; Theoretical result; Thermal decompositions; Thermal dissociation; Three parameters; Trajectory approach; Transition state; Transition state theories; Transition state theory; Abstracting; Dissociation; Electronic structure; Ethers; Fuels; Light sources; Organic compounds; Potential energy; Potential energy surfaces; Pyrolysis; Quantum chemistry; Shock tubes; Experiments; dimethyl ether; radical; ab initio calculation; article; controlled study; decomposition; dissociation; light; pressure; priority journal; temperature; theory; thermal reaction; Ab initio; Abstraction; H+ dimethyl ether; Shock tube; Transition state theory
International Standard Serial Number (ISSN)
Article - Journal
© 2011 Elsevier, All rights reserved.
01 Apr 2011