Influence of transition state resonances on integral cross sections and product rovibrational distributions for the Cl+HCl r arrow ClH+Cl reaction

Journal Article · Fri Mar 15 04:00:00 EST 1991 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.460617· OSTI ID:5733282

Schatz, G C ^[1]; Sokolovski, D; Connor, J N.L. ^[2]

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1. Theoretical Chemistry Group, Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (US)
2. Department of Chemistry, University of Manchester, Manchester M13 9PL (England)

An accurate quantum scattering calculation for the Cl+HCl{r arrow}ClH+Cl reaction has been performed. In particular, we study the influence of the lowest transition state resonance on the energy dependence of the state-to-state integral cross sections and product rovibrational distributions. The calculations use a recently developed centrifugal sudden hyperspherical (CSH) coordinate reactive scattering code. The Bondi--Connor--Manz--Roemelt semiempirical potential energy surface is employed. All 161 partial waves needed for the convergence of the cross sections are included in the calculations. We find that the resonance perturbs certain reagent and product rotational levels of the vibrational ground state ({ital v}=0, {ital j}=14--16), as well as all open rotational levels ({ital j}=0--8) of the first vibrationally excited state ({ital v}=1). Transitions from the ground reagent to the ground product vibrational state, such as {ital v}=0, {ital j}=15{r arrow}{ital v}{prime}=0, {ital j} {prime}=15, show almost no resonance structure in the integral cross sections; rather direct scattering dominates the partial wave sum. On the other hand, transitions between perturbed {ital v}=0 rotational states and any {ital v}{prime}=1 rotational state, or between any {ital v}=1 state and perturbed {ital v}{prime}=0 states, or between any {ital v}=1 and any {ital v}{prime}=1 state, show a novel resonance feature in the integral cross sections. This novel feature is a sudden smooth step'' in the integral cross section, centered at the resonance energy for the partial wave with zero total angular momentum quantum number ({ital J}=0). The step has a width equal to the {ital J}=0 resonance width. Sometimes this step is superimposed on a slowly varying background which arises from direct scattering.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 5733282
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 94:6; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ANL
ATOM COLLISIONS
ATOM-MOLECULE COLLISIONS
CHEMICAL REACTION KINETICS
CHLORINE
COLLISIONS
CROSS SECTIONS
ELEMENTS
ENERGY LEVELS
EXCITED STATES
HALOGENS
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
INORGANIC ACIDS
INTEGRAL CROSS SECTIONS
KINETICS
MOLECULE COLLISIONS
NATIONAL ORGANIZATIONS
NONMETALS
REACTION KINETICS
ROTATIONAL STATES
US AEC
US DOE
US ERDA
US ORGANIZATIONS
VIBRATIONAL STATES