MECHANISM AND KINETICS OF THE CH3CH2C(O)OCH2CH3+OH REACTION: A THEORETICAL STUDY

作者：Hou, Cong; Ci, Cheng-Gang; Jin, Tong-Yin; Wang, Yong-Xia; Liu, Jing-Yao^*

来源：Journal of Theoretical and Computational Chemistry, 2011, 10(5): 691-709.

DOI：10.1142/S0219633611006736

• Dual-level direct dynamics method
• ethyl propanoate
• rate constant
• variational transition-state theory

The hydrogen abstraction reaction of CH3CH2C(O)OCH2CH3 + OH has been studied theoretically by dual-level direct dynamics method. Six H-abstraction channels were found for this reaction. The required potential energy surface information for the kinetic calculations was obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants were calculated by the improved canonical variational transition-state theory with small-curvature tunneling correction (ICVT/SCT) approach in the temperature range of 200-2000 K. It is shown that the "methylene H-abstraction" from the alkoxy end of the ester CH3CH2C(O)OCH2CH3 is the dominant channel at lower temperature (< 400K), while the other channels from the acetyl end should be taken into account as the temperature increases and become the competitive ones at higher temperature. The calculated global rate constants are in good agreement with the experimental ones in the measured temperature range and exhibit a negative temperature dependence below 500K. A four-parameter rate constant expression was fitted from the calculated kinetic data between 200-2000 K.

• 出版日期2011-10
• 单位吉林大学