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Rydberg and valence state excitation dynamics: a velocity map imaging study involving the E-V state interaction in HBr

Photoexcitation dynamics of the E( 1 Σ + ) ( v ′ = 0) Rydberg state and the V( 1 Σ + ) ( v ′) ion-pair vibrational states of HBr are investigated by velocity map imaging (VMI). H + photoions, produced through a number of vibrational and rotational levels of the two states were imaged and kinetic ene...

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Published in:Physical chemistry chemical physics : PCCP 2015-04, Vol.17 (16), p.1468-1477
Main Authors: Zaouris, Dimitris, Kartakoullis, Andreas, Glodic, Pavle, Samartzis, Peter C, Rafn Hróðmarsson, Helgi, Kvaran, Ágúst
Format: Article
Language:English
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Summary:Photoexcitation dynamics of the E( 1 Σ + ) ( v ′ = 0) Rydberg state and the V( 1 Σ + ) ( v ′) ion-pair vibrational states of HBr are investigated by velocity map imaging (VMI). H + photoions, produced through a number of vibrational and rotational levels of the two states were imaged and kinetic energy release (KER) and angular distributions were extracted from the data. In agreement with previous work, we found the photodissociation channels forming H*( n = 2) + Br( 2 P 3/2 )/Br*( 2 P 1/2 ) to be dominant. Autoionization pathways leading to H + + Br( 2 P 3/2 )/Br*( 2 P 1/2 ) via either HBr + ( 2 Π 3/2 ) or HBr + *( 2 Π 1/2 ) formation were also present. The analysis of KER and angular distributions and comparison with rotationally and mass resolved resonance enhanced multiphoton ionization (REMPI) spectra revealed the excitation transition mechanisms and characteristics of states involved as well as the involvement of the E-V state interactions and their v ′ and J ′ dependence. Velocity map imaging and REMPI of HBr reveal multiphoton excitation mechanisms and the involvement of the Rydberg state in valence state interactions.
ISSN:1463-9076
1463-9084
DOI:10.1039/c5cp00748h