Strong collision rate coefficients in unimolecular reaction rate theory

Nordholm, Sture; Schranz, Harold W.

doi:10.1016/0301-0104(81)85139-7

Cited by 12 publications

(1 citation statement)

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“…Figure 2 gives plots of k / k *, where k refers to the normal isotopomer, vs. log( p ) values for the four reactions at 500 K. For unimolecular reactions of large molecules with low activation energies at elevated temperatures, the traditional form of the SCA–RRKM formalism used here is likely to be inaccurate 40 at intermediate collision frequencies between the first‐ and second‐order regions. However, Nordholm and Schranz 40 have shown that this treatment is accurate in the low‐ and high‐pressure extremes. We are dealing here with small molecules at relatively low temperatures.…”

Section: Kinetic Isotope Effectsmentioning

confidence: 99%

C₃H₄: Density functional study of interconversion of isomers

Kakkar

2003

Int J of Quantum Chemistry

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ABSTRACT:The B3LYP density functional has been used to calculate the reaction paths for the interconversion of the three stable isomers of C 3 H 4 , namely, propyne, allene, and cyclopropene, and the results compared with experimental data. It is found that the trans nonplanar isomer of vinylmethylene plays a central role in the interconversions. Other thermochemical parameters, like the entropies of reaction and activation, have also been calculated. The rate constants of the various competing reactions have been calculated using the Rice-Ramsperger-Kassel-Marcus theory. Kinetic isotope effects for the reactions have also been investigated to gain an insight into their mechanisms.

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Section: Kinetic Isotope Effectsmentioning

confidence: 99%