Classical functional sensitivity analysis of the collinear F+H/sub 2/ reaction

Journal Article · Wed Feb 15 04:00:00 EST 1989 · J. Chem. Phys.; (United States)

OSTI ID:6548931

Judson, R S; Rabitz, H

The method of classical functional sensitivity analysis (CFSA) is applied to the collinear F+H/sub 2/ reaction and its isotopic analogues. The effects of features in the Muckerman 5 (M5) potential upon product vibrational energy are examined using constant energy ensembles (1 and 5 kcal/mol) with H/sub 2/(v = 0) and H/sub 2/(v = 1). The same is done using thermal averaged ensembles at 300, 400, 1000, and 1500 K. Two significant results are reported. First, at low energies and at even relatively high temperatures (1000 K), the region of the potential to which the reactive product vibrational energy is most sensitive is the vicinity of the saddle point. In addition, the sensitivity function is smooth and nonoscillatory there. Second, at high temperatures and energies, the sensitivity function becomes oscillatory in magnitude and sign over the entire interaction region. The implications which these results have for methods which fit a potential to experimental data are discussed.

• Research Organization: Department of Chemistry, Princeton University, Princeton, New Jersey 08540
• OSTI ID: 6548931
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 90:4; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
657002* -- Theoretical & Mathematical Physics-- Classical & Quantum Mechanics
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
74 ATOMIC AND MOLECULAR PHYSICS
CHEMICAL REACTION KINETICS
CLASSICAL MECHANICS
ELEMENTS
FLUORINE
HALOGENS
HYDROGEN
KINETICS
MECHANICS
NONMETALS
POTENTIALS
QUANTUM MECHANICS
REACTION KINETICS
SENSITIVITY ANALYSIS