Multiphoton dissociative ionization of tert-pentyl bromide near 265 nm

Mao, Rui; Zhang, Qun; Zang, Jianzheng; He, Chao; Chen, Min; Chen, Yang

doi:doi:10.1063/1.3671368

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We report on the photodissociation dynamics of tert-pentyl bromide near 265 nm investigated by time-sliced velocity map imaging. The speed and angular distributions have been analyzed for both the ground-state Br(²P_3/2) atom (denoted Br) and the spin–orbit excited-state Br(²P_1/2) atom (denoted Br*). The speed distributions of Br and Br* atoms are all found to consist of three Gaussian components, which correlate to three independent dissociation pathways on the excited potential energy surfaces: (1) the high translational energy (E_T) component from the prompt dissociation along the C–Br stretching mode, (2) the middle E_T component from the repulsive mode along the C–Br stretching coupled with some bending motions, and (3) the low E_T component from the repulsive mode along the C–Br stretching coupled with more bending motions. More interestingly, we have also observed the tert−C₅H11+ ions in 263–267 nm. The near-zero kinetic energy distributions extracted from the three tert−C₅H11+ images near 265 nm show the typical characteristics that are attributable to multiphoton dissociative ionization, suggesting the existence of a neutral superexcited state of the parent tert-pentyl bromide molecule. The contribution of bromine atoms formed in this dissociative ionization channel adds in the total relative distribution of low E_T component in the Br*(Br) formation channel, which reasonably explains the abnormal distributions observed in between the middle and low E_T components in the Br*(Br) formation channel.

Article Outline

INTRODUCTION
EXPERIMENT
RESULTS
DISCUSSION
1. Bromine atoms
2. tert−C₅H11+ ions
CONCLUSIONS

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KEYWORDS and PACS

Keywords

excited states, ground states, multiphoton processes, organic compounds, photodissociation, potential energy surfaces

PACS

33.80.Gj

Diffuse spectra; predissociation, photodissociation
33.80.Rv

Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states)
31.50.Bc

Potential energy surfaces for ground electronic states
31.50.Df

Potential energy surfaces for excited electronic states

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3671368

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef

American Institute of Physics

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