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Issue 47, 2014
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Imaging the stereodynamics of methyl iodide photodissociation in the second absorption band: fragment polarization and the interplay between direct and predissociation

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Abstract

The stereochemistry of methyl iodide photodissociation in the onset of the second absorption B-band has been studied using slice imaging of the CH3(ν = 0) and I*(2P1/2) photoproducts. The stereodynamical data have been crucial to disentangle the photochemistry of methyl iodide in terms of the competition between direct dissociation and electronic predissociation. The origin of the B-band has been established with high accuracy at 201.11 ± 0.12 nm and a depolarization factor due to parent molecule rotation during predissociation has been found to be 0.29 ± 0.06. Analysis of the semiclassical Dixon's bipolar moments extracted from the CH3(ν = 0) sliced images indicates that direct excitation to the A-band 3A1 repulsive state in the vicinity of the origin of the B-band is remarkably enhanced by vibrational coupling between the electronic states involved at the conical intersection through in-plane vibrational motion of the molecule.

Graphical abstract: Imaging the stereodynamics of methyl iodide photodissociation in the second absorption band: fragment polarization and the interplay between direct and predissociation

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Publication details

The article was received on 26 Aug 2014, accepted on 16 Oct 2014 and first published on 22 Oct 2014


Article type: Paper
DOI: 10.1039/C4CP03823A
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Citation: Phys. Chem. Chem. Phys., 2014,16, 26330-26341

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    Imaging the stereodynamics of methyl iodide photodissociation in the second absorption band: fragment polarization and the interplay between direct and predissociation

    M. G. González, J. D. Rodríguez, L. Rubio-Lago and L. Bañares, Phys. Chem. Chem. Phys., 2014, 16, 26330
    DOI: 10.1039/C4CP03823A

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