Reactions probabilities, resonances, and thermal rate constants for the collinear reactins H + FH and D + FD on a low-barrier surface. Close-coupling and tunneling calculations, variational
- Univ. of Minnesota, Minneapolis
We study the collinear H + FH ..-->.. HF + H and D + FD ..-->.. DF + D reactions on a potential-energy surface that has twin 1.75 kcal/mol saddle points. We present accurate quantal reaction probabilities over a wide energy range, including three resonance energies and three resonance widths for each isotopic case. From these we calculate accurate quantal rate constants at temperatures 75 to 7000 K for H + FH and 75 to 2400 K for D + FD; and we separate out the contributions of the lowest-energy resonance to the low-temperature rates. We present plots of S-matrix phases and eigenphases and Argand diagrams. The accurate quantal results are used to test a wide variety of approximate dynamical results: semiclassical and quantal resonance calculations based on the vibrationally adiabatic model; rate constants calculated by conventional transition-state theory, three versions of variational transition-state theory, and the unified statistical model; and vibrationally adiabaic transmission coefficients.
- DOE Contract Number:
- AC02-79ER10425
- OSTI ID:
- 5772105
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:25; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ADIABATIC PROCESSES
ARGAND DIAGRAMS
CALCULATION METHODS
DATA
DEUTERIUM
DIAGRAMS
ELEMENTS
ENERGY
HYDROFLUORIC ACID
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
INORGANIC ACIDS
ISOTOPES
KINETICS
LIGHT NUCLEI
MATHEMATICAL MODELS
MECHANICS
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
POTENTIAL ENERGY
PROBABILITY
QUANTUM MECHANICS
REACTION KINETICS
RESONANCE
SCATTERPLOTS
STABLE ISOTOPES
STATISTICAL DATA
TEMPERATURE EFFECTS
THEORETICAL DATA