Volume 238, 2022

The unimolecular decomposition of dimethoxymethane: channel switching as a function of temperature and pressure

Abstract

Branching ratios of competing unimolecular reactions often exhibit a complicated temperature and pressure dependence that makes modelling of complex reaction systems in the gas phase difficult. In particular, the competition between steps proceeding via tight and loose transition states is known to present a problem. A recent example from the field of combustion chemistry is the unimolecular decomposition of CH3OCH2OCH3 (DMM), which is discussed as an alternative fuel accessible from sustainable sources. It is shown by a detailed master equation analysis with energy- and angular-momentum-resolved specific rate coefficients from RRKM theory and from the simplified statistical adiabatic channel model, how channel switching of DMM depends on temperature and pressure, and under which experimental conditions which channels prevail. The necessary molecular and energy data were obtained from quantum-chemical calculations at the CCSD(F12*)(T*)/cc-pVQZ-F12//B2PLYP-D3/def2-TZVPP level of theory. A parameterization describing the channel branching over extended ranges of temperature and pressure is derived, and the model is used to simulate shock tube experiments with detection by atomic resonance absorption spectroscopy and time-of-flight mass spectrometry. The agreement between the simulated and experimental concentration–time profiles is very good. The temperature and pressure dependence of the channel branching is rationalized, and the data are presented in a form that can be readily implemented into DMM combustion models.

Graphical abstract: The unimolecular decomposition of dimethoxymethane: channel switching as a function of temperature and pressure

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
09 Feb 2022
Accepted
31 Mar 2022
First published
31 Mar 2022
This article is Open Access
Creative Commons BY license

Faraday Discuss., 2022,238, 665-681

The unimolecular decomposition of dimethoxymethane: channel switching as a function of temperature and pressure

T. M. Pazdera, J. Wenz and M. Olzmann, Faraday Discuss., 2022, 238, 665 DOI: 10.1039/D2FD00039C

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