Theoretical study of the reaction mechanism of 2-metyhlthiophene with NO3 radical
CHEN Long, WANG Weina*, LU Tianyu, WANG Wenliang
(Key Laboratory for Macromolecular Science of Shaanxi Province, College of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi′an 710119, Shaanxi, China)
Abstract:
The reaction mechanism of 2-metyhlthiophene with NO3 radical have been investigated at the B3LYP/6-311++G(3df,2pd)//B3LYP/6-31+G(d,p) level of theory. The results show that the title reaction mainly includes hydrogen abstraction, SN2 substitution and addition-elimination reactions. The barriers of SN2 substitution and addition-elimination are higher than the hydrogen abstraction reactions, in which the barrier of R4 is equal to 6.77 kJ/mol and it is a dominant pathway in the title reactions. The rate constant for the dominant channel R4 is calculated with conventional transition state theory (TST) at 298 K, where Wigner method is adopted to correct the quantum mechanical tunneling effect. The calculated value is 1.03×10-13 cm3/(molecule·s), which is consistent with Cabaas′s result (7.21×10-13 cm3/(molecule·s)) by using laser induced fluorescence method.
KeyWords:
2-methylthiophene; NO3 ; reaction mechanism; rate constant
