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Title: Communication: Direct measurements of nascent O({sup 3}P{sub 0,1,2}) fine-structure distributions and branching ratios of correlated spin-orbit resolved product channels CO(ã{sup 3}Π; v) + O({sup 3}P{sub 0,1,2}) and CO(Χ{sup ~1}Σ{sup +}; v) + O({sup 3}P{sub 0,1,2}) in VUV photodissociation of CO{sub 2}

We present a generally applicable experimental method for the direct measurement of nascent spin-orbit state distributions of atomic photofragments based on the detection of vacuum ultraviolet (VUV)-excited autoionizing-Rydberg (VUV-EAR) states. The incorporation of this VUV-EAR method in the application of the newly established VUV-VUV laser velocity-map-imaging-photoion (VMI-PI) apparatus has made possible the branching ratio measurement for correlated spin-orbit state resolved product channels, CO(ã{sup 3}Π; v) + O({sup 3}P{sub 0,1,2}) and CO(Χ{sup ~1}Σ{sup +}; v) + O({sup 3}P{sub 0,1,2}), formed by VUV photoexcitation of CO{sub 2} to the 4s(1{sub 0}{sup 1}) Rydberg state at 97,955.7 cm{sup −1}. The total kinetic energy release (TKER) spectra obtained from the O{sup +} VMI-PI images of O({sup 3}P{sub 0,1,2}) reveal the formation of correlated CO(ã{sup 3}Π; v = 0–2) with well-resolved v = 0–2 vibrational bands. This observation shows that the dissociation of CO{sub 2} to form the spin-allowed CO(ã{sup 3}Π; v = 0–2) + O({sup 3}P{sub 0,1,2}) channel has no potential energy barrier. The TKER spectra for the spin-forbidden CO(Χ{sup ~1}Σ{sup +}; v) + O({sup 3}P{sub 0,1,2}) channel were found to exhibit broad profiles, indicative of the formation of a broad range of rovibrational states of CO(Χ{sup ~1}Σ{sup +})  with significant vibrational populations for vmore » = 18–26. While the VMI-PI images for the CO(ã{sup 3}Π; v = 0–2) + O({sup 3}P{sub 0,1,2}) channel are anisotropic, indicating that the predissociation of CO{sub 2} 4s(1{sub 0}{sup 1}) occurs via a near linear configuration in a time scale shorter than the rotational period, the angular distributions for the CO(Χ{sup ~1}Σ{sup +}; v) + O({sup 3}P{sub 0,1,2}) channel are close to isotropic, revealing a slower predissociation process, which possibly occurs on a triplet surface via an intersystem crossing mechanism.« less
Authors:
; ; ; ; ; ;  [1]
  1. Department of Chemistry, University of California, Davis, Davis, California 95616 (United States)
Publication Date:
OSTI Identifier:
22420120
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 23; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANGULAR DISTRIBUTION; ANISOTROPY; CARBON DIOXIDE; CARBON MONOXIDE; FINE STRUCTURE; KINETIC ENERGY; OXYGEN IONS; PHOTOLYSIS; PREDISSOCIATION; RYDBERG STATES; SPECTRA; SPIN; VIBRATIONAL STATES