Intramolecular energy transfer in the HNC/HCN isomerization reaction: Quasiclassical state specific isomerization rates controlled by localized potential features

Journal Article · Wed Apr 15 00:00:00 EDT 1987 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.452719· OSTI ID:6773097

Smith, R S; Shirts, R B; Patterson, C W

A model of the HCN molecule with two degrees of freedom, consisting of the H--NC stretch and the H--NC bend with the CequivalentN distance held fixed, was studied. The semiclassical technique of adiabatic switching was used to obtain trajectories at eigenvalues of metastable states of the system. Quasiclassical results for the isomerization rate from HNC to HCN at various stretch and bend excitations are given. Results show that the isomerization rate is highly dependent on the bend excitation and less so on the total energy of the system in contradiction to predictions of statistical theories. Examination of individual trajectories and surfaces of section reveal the development of chaos near the N/sub bend/ = 6 level. The development of chaos is apparently responsible for the energy transfer between the modes and thus the isomerization rate. Examination of the potential surface reveals a distinct topological change near the N/sub bend/ = 6 level. The region responsible for energy transfer is identified, and the possible mechanisms for this transfer are enumerated.

• Research Organization: Los Alamos National Laboratory, T-12, Mail Stop J569, Los Alamos, New Mexico 87545 and Department of Chemistry, University of Utah, Salt Lake City, Utah 84112
• OSTI ID: 6773097
• Journal Information: J. Chem. Phys.; (United States), Vol. 86:8
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HYDROCYANIC ACID
ENERGY TRANSFER
ISOMERIZATION
ISOCYANIC ACID
CHEMICAL REACTION KINETICS
MOLECULAR MODELS
SEMICLASSICAL APPROXIMATION
VIBRATIONAL STATES
CARBONIC ACID DERIVATIVES
CHEMICAL REACTIONS
CYANIDES
ENERGY LEVELS
EXCITED STATES
HYDROGEN COMPOUNDS
INORGANIC ACIDS
KINETICS
MATHEMATICAL MODELS
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
REACTION KINETICS
400201* - Chemical & Physicochemical Properties