Abstract
Practical aspects of implementing tunneling contributions into unimolecular reactions of polyatomic molecules are discussed. One-dimensional expressions of transmission coefficients for allowed and forbidden reactions are combined with statistical unimolecular rate expressions. Specific rate constants k(E), thermally averaged high pressure rate constants k∞ and low pressure fall-off rate coefficients are elaborated. The dissociation reactions of H2CO and N2O and intramolecular hydrogen shifts in large polyatomic molecules are used as experimental examples. Identifying the allowed or forbidden character and separating tunneling from statistical factors presents a most difficult problem in most practical cases.
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Troe, J. (1986). Some Practical Aspects of Tunneling in Unimolecular Reactions. In: Jortner, J., Pullman, B. (eds) Tunneling. The Jerusalem Symposia on Quantum Chemistry and Biochemistry, vol 19. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4752-8_12
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DOI: https://doi.org/10.1007/978-94-009-4752-8_12
Publisher Name: Springer, Dordrecht
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