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Potential Energy Surfaces and Dynamics Calculations pp 375–420Cite as

Reactive Scattering Resonances and their Physical Interpretation: The Vibrational Structure of the Transition State

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Abstract

Quantum mechanical structure in reaction-probability-versus-energy curves for a realistic potential energy surface was first observed about a decade ago,1,2 for the collinear H + H2 system. Such structure had been previously found for a potential energy surface having sharp edges,3 made of piecewise-constant potentials, but in one-mathematical-dimensional (1MD) barrier problems, structure in transmission-probability-versus-energy curves4 is known to disappear when a rectangular barrier is replaced by one which is sufficiently “rounded”, such as parabolic5,6 or Eckart6,7 barriers, and is attributed to edge diffraction effects. The structure in the collinear H + H2 results on a smoothly varying surface, at energies above the vibrational excitation threshold of reaction products, was guessed1b as being due to interference effects between different reaction paths, a guess subsequently confirmed by a quantum mechanical lifetime analysis8 and a semiclassical calculation.9 The former indicated the concomitant presence of and interference between direct and dynamic resonance (Feshbach10) processes. The mechanism of such resonances was attributed to the existence of wells in the vibrationally adiabatic potentials along the minimum energy path.2b

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Authors and Affiliations

  1. Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA, 91125, USA

    Aron Kuppermann

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  1. Aron Kuppermann
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  1. University of Minnesota, Minneapolis, Minnesota, USA

    Donald G. Truhlar

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Kuppermann, A. (1981). Reactive Scattering Resonances and their Physical Interpretation: The Vibrational Structure of the Transition State. In: Truhlar, D.G. (eds) Potential Energy Surfaces and Dynamics Calculations. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-1735-8_16

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  • DOI: https://doi.org/10.1007/978-1-4757-1735-8_16

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  • Print ISBN: 978-1-4757-1737-2

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