Femtosecond predissociation dynamics of the methyl radical from the 3p z Rydberg state

The real time dynamics of electronic predissociation of the CH 3 radical (and its deuterated variant CD 3 ) from selected vibrational states of the 3p z Rydberg state have been measured for the first time using a novel methodology based on a femtosecond three-color experiment to generate, two-photon...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2016, Vol.18 (1), p.110-118
Main Authors: Balerdi, Garikoitz, Woodhouse, Joanne, Zanchet, Alexander, de Nalda, Rebeca, Senent, María L., García-Vela, Alberto, Bañares, Luis
Format: Article
Language:English
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Summary:The real time dynamics of electronic predissociation of the CH 3 radical (and its deuterated variant CD 3 ) from selected vibrational states of the 3p z Rydberg state have been measured for the first time using a novel methodology based on a femtosecond three-color experiment to generate, two-photon excite and ionize methyl radicals as a function of time in combination with velocity map imaging detection. Subpicosecond lifetimes have been measured, showing a decreasing trend as vibrational excitation in the symmetric stretch and bending umbrella modes increases for both species. High-level ab initio calculations have been carried out in order to elucidate the CH 3 3p z predissociation mechanism and support the lifetime measurements. The observed lifetimes are relevant for the understanding of the resonance enhanced multiphoton ionization spectroscopy of this radical.
ISSN:1463-9076
1463-9084
DOI:10.1039/C5CP05710H