Quantum mechanical calculations on the systems HF(v) + H and HF(v) + D on a realistic potential energy surface

Journal Article · Thu Nov 17 04:00:00 EST 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100334a024· OSTI ID:6222002

Kaye, J A; Kuppermann, A; Dwyer, J P

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), Journal Name: J. Phys. Chem.; (United States) Vol. 92:23; ISSN JPCHA
• Country of Publication: United States
• Language: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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54 ENVIRONMENTAL SCIENCES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DEUTERIUM
ELEMENTS
ENERGY LEVELS
EXCITED STATES
HYDROFLUORIC ACID
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
INORGANIC ACIDS
ISOTOPES
KINETICS
LIGHT NUCLEI
MECHANICS
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
POTENTIALS
QUANTUM MECHANICS
REACTION KINETICS
RYDBERG STATES
STABLE ISOTOPES
THEORETICAL DATA
VIBRATIONAL STATES