Measurements and quasi-quantum modeling of the steric asymmetry and parity propensities in state-to-state rotationally inelastic scattering of NO (2?1/2) with D2.

Relative integrated cross sections are measured for spin-orbit-conserving, rotationally inelastic scattering of NO

Conclusions and Recommendations

Rosana G. Moreira, Editor-in-Chief; Texas A&M UniversityThis is a paper from International Commission of Agricultural Engineering (CIGR, Commission Internationale du Genie Rural) E-Journal Volume 7 (2005): Conclusions and Recommendations by E. Gasparett

Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO(2?1/2) with He.

Contains fulltext : 13854.pdf (publisher's version ) (Open Access

Infrared absorption measurements of the kinetics of Cl atom reactions with C{sub 3}H{sub n} (n=4,6) unsaturated hydrocarbons between 300-850 K

The reaction of chlorine (Cl) atoms with the unsaturated C{sub 3}H{sub n} where n=4,6, hydrocarbons propylene, allene, and methyl acetylene have been uninvestigated as a function of temperature and pressure

Quantum Interference as the Source of Steric Asymmetry and Parity Propensity Rules in NO-Rare Gas Inelastic Scattering

Rotationally inelastic scattering of rare gas atoms and oriented NO molecules exhibits a remarkable alternation in the sign of steric asymmetry between even and odd changes in rotational quantum number. This effect has also been found in full quantum-mechanical scattering calculations. However, until now no physical picture has been given for the alternation. In this work, a newly developed quasi-quantum treatment (QQT) provides the first demonstration that quantum interferences between different orientations of the repulsive potential (that are present in the oriented wave function) are the source of this alternation. Further, from application of the treatment to collisions of nonoriented molecules, a previously unrecognized propensity rule is derived. The angular dependence of the cross sections for excitation to neighboring rotational states with the same parity is shown to be similar, except for a prefactor. Experimental results are presented to support this rule. Unlike conventional quantum-mechanical (or semiclassical) treatments, QQT requires no summation over the orbital angular momentum quantum number /or integration over the impact parameter b. This eliminates the need to solve large sets of coupled differential equations that couple /and rotational state channels among which interference can occur. The QQT provides a physical interpretation of the scattering amplitude that can be represented by a Legendre moment. Application of the QQT on a simple hard-shell potential leads to near-quantitative agreement with experimental observations. © 2006 American Chemical Society

A general scaling rule for the collision energy dependence of a rotationally inelastic differential cross-section and its application to NO(X) plus He

International audienceThe quasi-quantum treatment (QQT) (Gijsbertsen et al., J. Am. Chem. Soc., 2006, 128, 8777) provides a physically compelling framework for the evaluation of rotationally inelastic scattering, including the differential cross sections (DCS). In this work the QQT framework is extended to treat the DCS in the classically forbidden region as well as the classically allowed region. Most importantly, the QQT is applied to the collision energy dependence of the angular distributions of these DCSs. This leads to an analytical formalism that reveals a scaling relationship between the DCS calculated at a particular collision energy and the DCS at other collision energies. This scaling is shown to be exact for QM calculated or experimental DCSs if the magnitude of the (kinematic apse frame) underlying scattering amplitude depends solely on the projection of the incoming momentum vector onto the kinematic apse vector. The QM DCSs of the NO(X)-He collision system were found to obey this scaling law nearly perfectly for energies above 63 meV. The mathematical derivation is accompanied by a mechanistic description of the Feynman paths that contribute to the scattering amplitude in the classically allowed and forbidden regions, and the nature of the momentum transfer during the collision process. This scaling relationship highlights the nature of (and limits to) the information that is obtainable from the collision-energy dependence of the DCS, and allows a description of the relevant angular range of the DCSs that embodies this information