Abstract

The reaction path Hamiltonian model recently formulated by Miller, Handy, and Adams [J. Chem. Phys. 72, 99 (1980)] is applied to the unimolecular isomerization HNC→HCN. The reaction path, and the energy and force constant matrix along it, are calculated at the SCF level with a large basis set (’’double zeta plus polarization’’), and the microcanonical rate constant k(E) is computed in the energy range near and below the classical threshold of the reaction. It is seen, for example, that rates as fast as 105 sec−1 can occur at energies ∼8 kcal/mole below the classical threshold.

Keywords

IsomerizationReaction rate constantChemistryHamiltonian (control theory)Quantum tunnellingComputational chemistryPhysical chemistryPhysicsQuantum mechanicsKineticsOrganic chemistryMathematics

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Publication Info

Year
1980
Type
article
Volume
73
Issue
6
Pages
2733-2750
Citations
113
Access
Closed

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Stephen K. Gray, William H. Miller, Y. Yamaguchi et al. (1980). Reaction path Hamiltonian: Tunneling effects in the unimolecular isomerization HNC→HCN. The Journal of Chemical Physics , 73 (6) , 2733-2750. https://doi.org/10.1063/1.440494

Identifiers

DOI
10.1063/1.440494