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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 |
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Main Authors: | , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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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. |
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ISSN: | 1463-9076 1463-9084 |
DOI: | 10.1039/c5cp00748h |