Quantum theory of photodetachment spectra of transition states

Journal Article · Thu Aug 09 04:00:00 EDT 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100379a005· OSTI ID:6381120

Schatz, G C ^[1]

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1. Northwestern Univ., Evanston, IL (USA) Argonne National Laboratory, IL (USA)

Photodetachment of ions of the type XHY{sup {minus}} where X and Y are halogens produces the unstable neutral species XHY at a geometry that is often close to the transition state for the X + HY {yields} XH + Y reaction. The photodetachment spectra generally show a series of bands that can be interpreted as spectra of this transition state. This article discusses recent theoretical work that has attempted to interpret these spectra, with an emphasis on accurate three-dimensional quantum scattering calculations of the photodetachment spectra of ClHCl{sup {minus}} and IHI{sup {minus}}. The quantum scattering calculations use a recently developed hyperspherical coordinate based coupled channel method to calculate scattering wave functions and photodetachment Franck-Condon factors. Semiempirical potential energy surfaces have been used, and this provides a significant source of uncertainty in the theoretical analysis. In spite of this, the theoretical and experimental spectra are in reasonable agreement, with the same number of major peaks at about the same energies for both ClHCl{sup {minus}} and IHI{sup {minus}}. These peaks can arise from either transition-state resonances or direct scattering reactive thresholds.

• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6381120
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:16; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CALCULATION METHODS
CHARGED PARTICLES
ELEMENTS
FRANCK-CONDON PRINCIPLE
HALOGENS
IONS
NONMETALS
REACTION INTERMEDIATES
SPECTRA
THREE-DIMENSIONAL CALCULATIONS