Computational study on the kinetics of OH initiated oxidation of methyl difluoroacetate (CF sub(2)HCOOCH sub(3))

• Published in: Molecular physics Vol. 112; no. 14; pp. 1892 - 1898
• Main Authors: Singh, Hari Ji, Tiwari, Laxmi, Rao, Pradeep Kumar
• Format: Journal Article
• Language: English
• Published: 18.07.2014
• Subjects: Atmospheric pressure; Density; Mathematical analysis; Molecular physics; Rate constants; Reaction kinetics; Tunnelling
• ISSN: 0026-8976; 1362-3028
• DOI: 10.1080/00268976.2013.868554

The kinetics of hydrogen atom abstraction reactions of methyl difluoroacetate (CF sub(2)HCOOCH sub(3)) by OH radical has been studied by quantum mechanical method. The geometry optimisation and frequency calculation of the titled compound was performed with density functional theory using hybrid meta density functional MPWB1K with 6-31+G(d,p) basis set. Transition states have been determined and intrinsic reaction coordinate (IRC) calculation has been performed to ascertain that the transition from reactants to products was smooth through the corresponding transition state. Energy values are refined by making single point energy calculation at G3B3 level of theory and an energy level diagram is constructed. The standard enthalpies of formation of reactants and other species formed during the reaction were calculated using isodesmic method. The rate constants are calculated using canonical transition state theory and the overall rate constant is determined to be 1.3510 super(-13) cm super(3) molecule super(-1) s super(-1) at 298 K and 1 atmospheric pressure. Tunnelling has been taken into account in the determination of the rate constant because it plays a critical role at low temperature especially when transfer of hydrogen takes place. The calculated value is found to be in good agreement with the experimentally determined value of 1.4810 super(-13) cm super(3) molecule super(-1) s super(-1).