Characterization of exit-channel barriers for chemical reactions producing specific vibrational states

Journal Article · Sat Dec 15 04:00:00 EST 1984 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.447621· OSTI ID:5993904

Steckler, R; Truhlar, D G; Garrett, B C; Blais, N C; Walker, R B

Use of the reaction-path Hamiltonian in natural collision coordinates with WKB eigenvalues for stretching vibrations is tested for predicting state-specific vibrationally adiabatic barriers for the fully three-dimensional reaction F+D/sub 2/..-->..FD (n' = 4)+D. A range of potential energy surfaces, including one specifically designed to have no delayed threshold for the highest energetically allowed product vibrational state, are considered, and both approximate quantal scattering calculations and quasiclassical trajectory calculations are performed for comparison to the adiabatic predictions. We find that the adiabatic predictions correlate well with the quantal scattering results. We also study other features of the dynamics on the surface with no delayed vibrational threshold to see how changing the surface to eliminate the delayed threshold affects other reaction attributes. We find that the approximate quantal differential cross sections for this surface show an appreciable probability for forward scattering of the products. This trend is not exhibited by the quasiclassical trajectory calculations for the same surface.

• Research Organization: Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
• OSTI ID: 5993904
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 81:12; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
CROSS SECTIONS
DEUTERIUM
DIFFERENTIAL CROSS SECTIONS
ELEMENTS
ENERGY
ENERGY LEVELS
EXCITED STATES
FLUORINE
HALOGENS
HYDROGEN ISOTOPES
ISOTOPES
LIGHT NUCLEI
NONMETALS
NUCLEI
ODD-ODD NUCLEI
POTENTIAL ENERGY
STABLE ISOTOPES
VIBRATIONAL STATES
WKB APPROXIMATION