NIST Chemical Kinetics Database

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 + ·F → CH₂CN + HF
Reaction order:   2
Temperature:   200 - 2000 K
Rate expression:   2.96x10^-14 [cm³/molecule s] (T/298 K)^2.12 e^{3870 [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