Open AccessREACTION PATH HAMILTONIAN: TUNNELING EFFECTS IN THE UNIMOLECULAR ISOMERIZATION HNC u> HCN
Author(s) -
Stephen K. Gray,
William H. Miller,
Y. Yamaguchi,
Henry F. Schaefer III
Publication year - 1980
Publication title -
osti oai (u.s. department of energy office of scientific and technical information)
Language(s) - English
Resource type - Reports
DOI - 10.2172/1070021
Subject(s) - isomerization , chemistry , reaction rate constant , hamiltonian (control theory) , quantum tunnelling , computational chemistry , physics , quantum mechanics , kinetics , mathematics , organic chemistry , mathematical optimization , catalysis
The reaction path Hamiltonian model recently formulated by Miller, Handy, and Adams [J, Chern. Phys. 72, 99 (1980)] is applied to the unimolecular isomerization HNC {yields} 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 10{sup 5} sec{sup -1} can occur at energies ~ 8 kcal/mole below the classical threshold
Accelerating Research
Robert Robinson Avenue,
Oxford Science Park, Oxford
OX4 4GP, United Kingdom
Address
John Eccles HouseRobert Robinson Avenue,
Oxford Science Park, Oxford
OX4 4GP, United Kingdom