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Title: Rate coefficients of the CF3CHFCF3+H CF3CFCF3+H2 reaction at different temperatures calculated by transition state theory with ab initio and DFT reaction paths
Authors: Ng, M
Mok, DKW 
Lee, EPF
Dyke, JM
Keywords: Transition state theory
Ab inito calculations
Rate coefficient calculations
Issue Date: 2013
Publisher: Wiley-Blackwell
Source: Journal of computational chemistry, 2013, v. 34, no. 7, p. 545-557 How to cite?
Journal: Journal of Computational Chemistry 
Abstract: The minimum energy path (MEP) of the reaction, CF3CHFCF3 + H transition state (TS) CF3CFCF3 + H2, has been computed at different ab initio levels and with density functional theory (DFT) using different functionals. The computed B3LYP/6-31++G**, BH&HLYP/cc-pVDZ, BMK/6-31++G**, M05/6-31+G**, M05-2X/6-31+G**, UMP2/6-31++G**, PUMP2/6-31++G**//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVDZ//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVTZ(spd,sp)//UMP2//6-31++G**, RCCSD(T)/CBS//M05/6-31+G**, and RCCSD(T)/CBS//UMP2/6-31++G** MEPs, and associated gradients and Hessians, were used in reaction rate coefficient calculations based on the transition state theory (TST). Reaction rate coefficients were computed between 300 and 1500 K at various levels of TST, which include conventional TST, canonical variational TST (CVT) and improved CVT (ICVT), and with different tunneling corrections, namely, Wigner, zero-curvature, and small-curvature (SCT). The computed rate coefficients obtained at different ab initio, DFT and TST levels are compared with experimental values available in the 10001200 K temperature range. Based on the rate coefficients computed at the ICVT/SCT level, the highest TST level used in this study, the BH&HLYP functional performs best among all the functionals used, while the RCCSD(T)/CBS//MP2/6-31++G** level is the best among all the ab initio levels used. Comparing computed reaction rate coefficients obtained at different levels of theory shows that, the computed barrier height has the strongest effect on the computed reaction rate coefficients as expected. Variational effects on the computed rate coefficients are found to be negligibly small. Although tunneling effects are relatively small at high temperatures (approximate to 1500 K), SCT corrections are significant at low temperatures (approximate to 300 K), and both barrier heights and the magnitudes of the imaginary frequencies affect SCT corrections.
ISSN: 0192-8651
DOI: 10.1002/jcc.23163
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