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Accessibility information
Author(s):   Pei, K.M.; Li, H.Y.
Title:   Direct ab initio dynamics studies of hydrogen abstraction reaction: F + CH3CN -> HF + CH2CN
Journal:   J. Mol. Struct. (Theochem)
Volume:   676
Page(s):   105 - 108
Year:   2004
Reference type:   Journal article
Squib:   2004PEI/LI105-108

Reaction:   CH3CN + ·FCH2CN + HF
Reaction order:   2
Temperature:   200 - 2000 K
Rate expression:   2.96x10-14 [cm3/molecule s] (T/298 K)2.12 e3870 [J/mole]/RT
Category:  Theory
Data type:   Ab initio
Comments:   The potential energy surface for the reaction was calculated at the MP2/6-311+ G (d,p) level of theory. Energies along the minimum energy path were improved via QCISD (T) calculations. Thermal rate constants were calculated by a variety of transition state theory (TST) methods for the temperature range 200 - 2000 K. The best of these are the TST with small-curvature tunneling (TST/SCT) and these values are reported.

The units of Table 3 of the paper appear to be incorrectly stated as cm3/mol s instead of cm3/molecule s. The reported 3-parameter fit was calculated at NIST from the data in Table 3 of the paper and fits the reported values within about 4% over the temperature range of 200 - 2000 K.
Calculated rate constants at 300 K are a factor of 88 smaller than the experimental value of 1.25x10-11 cm3 molecule s (K. Hoyermann, J. Seeba, Z. Phys. Chem. 188 (1995) 215). Pei and Li incorrectly cite the experimental value from the above work as 6.14x10-13 cm3/ molecule s.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
200 1.30E-13
300 1.41E-13
400 1.77E-13
500 2.25E-13
600 2.83E-13
700 3.51E-13
800 4.29E-13
900 5.16E-13
1000 6.13E-13
1100 7.19E-13
1200 8.35E-13
1300 9.60E-13
1400 1.10E-12
1500 1.24E-12
1600 1.39E-12
1700 1.56E-12
1800 1.73E-12
1900 1.92E-12
2000 2.11E-12