Theoretical Studies on the Kinetics of Multi-Channel Gas-Phase Unimolecular Decomposition of Acetaldehyde
| العنوان: | Theoretical Studies on the Kinetics of Multi-Channel Gas-Phase Unimolecular Decomposition of Acetaldehyde |
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| المؤلفون: | S. Mohammad Ali Hosseini, S. Rasoul Hashemi, Vahid Saheb |
| المصدر: | The Journal of Physical Chemistry A. 121:6887-6895 |
| بيانات النشر: | American Chemical Society (ACS), 2017. |
| سنة النشر: | 2017 |
| مصطلحات موضوعية: | 010304 chemical physics, Chemistry, Thermal decomposition, Semiclassical physics, Thermodynamics, 010402 general chemistry, Kinetic energy, 01 natural sciences, Decomposition, 0104 chemical sciences, Transition state theory, Reaction rate constant, 0103 physical sciences, Potential energy surface, Physical chemistry, Physical and Theoretical Chemistry, Isomerization |
| الوصف: | Theoretical kinetic studies are performed on the multichannel thermal decomposition of acetaldehyde. The geometries of the stationary points on the potential energy surface of the reaction are optimized at the MP2(full)/6-311++G(2d,2p) level of theory. More accurate energies are obtained by single point energy calculations at the CCSD(T,full)/augh-cc-pVTZ+2df, CBS-Q and G4 levels of theory. Here, by application of steady-state approximation to the thermally activated species CH3CHO* and CH2CHOH* and performance of statistical mechanical manipulations, expressions for the rate constants for different product channels are derived. Special attempts are made to compute accurate energy-specific rate coefficients for different channels by using semiclassical transition state theory. It is found that the isomerization of CH3CHO to the enol-form CH2CHOH plays a significant role in the unimolecular reaction of CH3CHO. The possible products of the reaction are formed via unimolecular decomposition of CH3CHO and CH2... |
| تدمد: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.7b04771 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::d2f81964323c3cc8090d6619bb2dd2b8 https://doi.org/10.1021/acs.jpca.7b04771 |
| رقم الانضمام: | edsair.doi.dedup.....d2f81964323c3cc8090d6619bb2dd2b8 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15205215 10895639 |
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| DOI: | 10.1021/acs.jpca.7b04771 |