Initial vibrational energy level distributions determined by infra-red chemiluminescence

Kinetics of the F + CH4Reaction in the Temperature Range 184−406 K

“…It can be seen that a value around 2.50 is quite well reproduced by the various investigators who used a variety of techniques. Exceptions are the significantly lower values of Kompa and Wanner 6 and of Jonathan et al and the significantly higher value of Wagner et al , The average value of the results, without the exceptional low and high values and without including our results is 2.55 ± 0.18. Our value fits this average very well.…”

The atomic fluorine + molecular hydrogen potential energy surface: the ecstasy and the agony

“…A second (after Muckerman V) well-known semiempirical potential energy surface for F + H2 is the SE-1 surface of Polanyi and Schreiber.41 Like Muckerman V, the SE-1 surface was designed to yield classical trajectory simulations of the dynamics in good agreement with experimental findings. [30][31][32][33][34][35][36][37][38][39][40] Table IV indicates concurrence of the highest levels of theory that the H-H distance at the transition state is 0.77 A, confirming the early ab initio prediction of BOPS. For the F-H distance, the agreement among theoretical methods is less precise, with fourth-order perturbation theory giving 1.44 A and multireference Cl giving 1.48 A.…”

HF infrared chemiluminescence. Relative rate constants for hydrogen abstraction from hydrocarbons, substituted methanes, and inorganic hydrides

“…The total emission intensity is given by ( 1). Multiplying and dividing (1) by Eü=o[HF"] gives IT=[HF](^Vi) The rate constants relative to CH4 are obtained from ch4 (10) The primary data are still the total relative intensities derived from plots of 7T vs. RH and CH4. However, these intensities must be weighted by ^ ,for CH4 and the reagent to obtain & / 4• The relative populations derived from the low resolution spectra are shown in Tables I and II.…”