Quantum mechanical calculations on the systems HF(v) + H and HF(v) + D on a realistic potential energy surface
The rates of the reactions HF(v) + H and HF(v) + D as well as rates of vibrational deactivation of HF have been studied by collinear quantum mechanical calculations on a realistic on a realistic potential energy surface. The surface used has a 40 kcal/mol barrier to exchange, far greater than that used in most previous calculations and in the vicinity of that suggested by ab initio calculations and experiments. Attention is focused on the reactive processes in these systems, which are found to be of low probability except at high translational energies. At energies where the reaction probability first becomes large, vibrationally adiabatic processes dominate, but this is not true at energies where the reaction probability is very small or at energies well above those where the total probability becomes of order unity. The rate of the chemical reaction is enhanced dramatically by reagent vibrational excitation, although addition of one quantum of reagent vibrational energy lowers the threshold for reaction by far less than that amount. The relationship between vibrational and translational energy in promoting reaction is discussed, as is the relationship of the results of these calculations to experimental data.
- Research Organization:
- California Institute of Technology, Pasadena (USA)
- OSTI ID:
- 6222002
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 92:23
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
DEUTERIUM
CHEMICAL REACTIONS
HYDROFLUORIC ACID
HYDROGEN
CHEMICAL REACTION KINETICS
POTENTIALS
QUANTUM MECHANICS
RYDBERG STATES
THEORETICAL DATA
VIBRATIONAL STATES
DATA
ELEMENTS
ENERGY LEVELS
EXCITED STATES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
INORGANIC ACIDS
ISOTOPES
KINETICS
LIGHT NUCLEI
MECHANICS
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
REACTION KINETICS
STABLE ISOTOPES
400201* - Chemical & Physicochemical Properties
500100 - Environment
Atmospheric- Basic Studies- (-1989)