TY - JOUR
ID - 4576
TI - Hydrogen Abstraction Reaction of Hydroxyl Radical with 1,1-Dibromoethane and 1,2-Dibromoethane Studied by Using Semi-Classical Transition State Theory
JO - Physical Chemistry Research
JA - PCR
LA - en
SN - 2322-5521
AU - Saheb, Vahid
AU - Solimannejad, Mohammad
AD - Department of Chemistry, Shahid-Bahonar University of Kerman, Kerman 76169, Iran
AD - Quantum Chemistry Group, Department of Chemistry, Faculty of Sciences, Arak University, Arak 38156-8-8349, Iran
Y1 - 2014
PY - 2014
VL - 2
IS - 2
SP - 123
EP - 130
KW - dibromoethane
KW - hydroxyl Radical
KW - Ab initio
KW - Semi-classical transition state
KW - rate constants
DO - 10.22036/pcr.2014.4576
N2 - The hydrogen abstraction reaction by OH radical from CH2BrCH2Br (R1) and CH₃CHBr2 (R2) is investigated theoretically by semi-classical transition state theory. The stationary points for both reactions are located by using ωB97X-D and KMLYP density functional methods along with cc-pVTZ basis. Single-point energy calculations are performed at the QCISD(T) and CCSD(T) levels of theory with different basis sets. The results show that the activation energies are very sensitive to effects of electron correlation and basis set. In order to correct basis set effects on the calculated energetic, a correction factor (CF) is determined from the energy difference between the MP2/cc-pVTZ and MP2/aug-cc-pVTZ levels. xij vibrational anharmonicity coefficients, needed for semi-classical transition state theory, are calculated at the KMLYP/cc-pVTZ level of theory. Thermal rate coefficients are computed over the temperature range from 200 to 3000 K and they are shown to be in accordance with available experimental data. The computed rate constants for the reactions R1 and R2 are fitted to the equation k(T)=A T^n exp[-E(T+T_0 )/(T^2+ T_0^2 ) ].
UR - http://www.physchemres.org/article_4576.html
L1 - http://www.physchemres.org/article_4576_0231952fe9ac383581bc7a21c6bb5bbb.pdf
ER -