Electronic to vibration‐rotational‐translational energy transfer in the quenching of by CO has been studied with state of the art crossed atomic, molecular, and laser beam techniques at 0.16 eV initial kinetic energy, and by ab initio CI calculations for the potential energy surfaces involved in the process. Double differential quenching cross sections are measured as a function of scattering angle and energy transferred to the molecule. A pronounced structure in the energy transfer spectra as well as a partial backward scattering is attributed to two different mechanisms, a ’’direct’’ one and one which proceeds through ’’complex’’ formation. The observations are explained by the calculated potential energy surfaces (PES) for the first excited states and the ground state which exhibit two crossing seams below the 2.1 eV excitation energy: (i) one for colinear approach of on the carbon side of CO with its lowest energy 1.06 eV at responsible for the direct process and (ii) one for colinear approach of on the oxygen end of CO with 1.28 eV at and allowing the quenching after ’’complex’’ formation. The angularly integrated cross sections are maximal at an energy transferred to the molecule equivalent to five vibrational quanta. Comparison with bulk data suggests strong rotational excitation (two vibrational quanta in the average) as can be rationalized from the anisotropy of the PES near the crossing region. Total quenching cross sections and their temperature dependence can be explained by the absorbing sphere model using the calculated location and energy of the crossing seams.
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15 August 1982
Research Article|
August 15 1982
Stereochemical effects in the quenching of by CO: Crossed beam experiment and ab initio CI potential energy surfaces
Werner Reiland;
Werner Reiland
Institut für Molekülphysik der Freien, Universität Berlin, D 1000 Berlin, West Germany
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Hans‐Ulrich Tittes;
Hans‐Ulrich Tittes
Institut für Molekülphysik der Freien, Universität Berlin, D 1000 Berlin, West Germany
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Ingolf V. Hertel;
Ingolf V. Hertel
Institut für Molekülphysik der Freien, Universität Berlin, D 1000 Berlin, West Germany
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Vlasta Bonačić‐Koutecký;
Vlasta Bonačić‐Koutecký
Instititut für Physikalische Chemie der Freien Universität Berlin, D 1000 Berlin, West Germany
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Maurizio Persico
Maurizio Persico
Instititut für Physikalische Chemie der Freien Universität Berlin, D 1000 Berlin, West Germany
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J. Chem. Phys. 77, 1908–1920 (1982)
Citation
Werner Reiland, Hans‐Ulrich Tittes, Ingolf V. Hertel, Vlasta Bonačić‐Koutecký, Maurizio Persico; Stereochemical effects in the quenching of by CO: Crossed beam experiment and ab initio CI potential energy surfaces. J. Chem. Phys. 15 August 1982; 77 (4): 1908–1920. https://doi.org/10.1063/1.444044
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