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

Autor:	M. Gonzalez, J. D. Rodríguez, Luis Bañares, Luis Rubio-Lago
Rok vydání:	2014
Předmět:	Chemistry Repulsive state Photodissociation General Physics and Astronomy Conical intersection Photochemistry Molecular physics Dissociation (chemistry) chemistry.chemical_compound Absorption band Molecule Physical and Theoretical Chemistry Rotational–vibrational coupling Methyl iodide
Zdroj:	Phys. Chem. Chem. Phys.. 16:26330-26341
ISSN:	1463-9084 1463-9076
DOI:	10.1039/c4cp03823a
Popis:	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*((2)P1/2) 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 (3)A1 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.
Databáze:	OpenAIRE
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