Multiphoton dissociation dynamics of the indenyl radical at 248 nm and 193 nm

Erin N Sullivan; Bethan Nichols; Stephen von Kugelgen; Gabriel da Silva; Daniel M Neumark

doi:10.1063/1.5121294

Multiphoton dissociation dynamics of the indenyl radical at 248 nm and 193 nm

J Chem Phys. 2019 Nov 7;151(17):174303. doi: 10.1063/1.5121294.

Authors

Erin N Sullivan¹, Bethan Nichols¹, Stephen von Kugelgen¹, Gabriel da Silva², Daniel M Neumark¹

Affiliations

¹ Department of Chemistry, University of California, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
² Department of Chemical Engineering, University of Melbourne, Victoria 3010 Australia.

Abstract

Photofragment translational spectroscopy is used to investigate the unimolecular photodissociation of the indenyl radical (C₉H₇). C₉H₇ radicals are generated by photodetachment of C₉H₇ ^- anions and are dissociated at 248 nm (5.00 eV) and 193 nm (6.42 eV). The following product channels are definitively observed at both wavelengths: C₂H₂ + C₇H₅, C₂H₂ + C₃H₃ + C₄H₂, and C₂H₂ + C₂H₂ + C₅H₃. The three-body product channels are energetically inaccessible from single photon excitation at either dissociation wavelength. This observation, in combination with calculated dissociation rates and laser power studies, implies that all dissociation seen in this experiment occurs exclusively through multiphoton processes in which the initial C₉H₇ radical absorbs two photons sequentially prior to dissociation to two or three fragments. The corresponding translational energy distributions for each product channel peak well below the maximum available energy for two photons and exhibit similar behavior regardless of dissociation wavelength. These results suggest that all products are formed by internal conversion to the ground electronic state, followed by dissociation.

Grants and funding

S10 OD023532/OD/NIH HHS/United States