Rydberg spectra of <i>trans</i>-1,2-dibromoethylene

Shi, Weiyu; Lipson, R. H.

doi:10.1063/1.2805081

Cited by 4 publications

(1 citation statement)

References 31 publications

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“…For molecular systems, Rydberg spectroscopy has become a crucial tool to identify molecules and particularly to distinguish isomers. 39,42 Isomers are compounds that have the same molecular formula but different structure. Chemically, isomers can have quite different behaviors and, therefore, it is important to differentiate them.…”

Section: Applications In Other Fields Of Physicsmentioning

confidence: 99%

Introducing many-body physics using atomic spectroscopy

Krebs¹,

Pabst²,

Santra³

2014

American Journal of Physics

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Atoms constitute relatively simple many-body systems, making them suitable objects for developing an understanding of basic aspects of many-body physics. Photoabsorption spectroscopy is a prominent method to study the electronic structure of atoms and the inherent many-body interactions. In this article the impact of many-body effects on well-known spectroscopic features such as Rydberg series, Fano resonances, Cooper minima, and giant resonances is studied, and related many-body phenomena in other fields are outlined. To calculate photoabsorption cross sections the time-dependent configuration interaction singles (TDCIS) model is employed. The conceptual clearness of TDCIS in combination with the compactness of atomic systems allows for a pedagogical introduction to many-body phenomena.

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Section: Applications In Other Fields Of Physicsmentioning

confidence: 99%

Introducing many-body physics using atomic spectroscopy

Krebs¹,

Pabst²,

Santra³

2014

American Journal of Physics

View full text Add to dashboard Cite

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Photodissociation of the geometric isomers of 1,2-dibromoethylene

Shi

Staroverov

Lipson

2009

The Journal of Chemical Physics

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Resonance-enhanced multiphoton ionization (REMPI) spectra of 1,2-dibromoethylene (C(2)H(2)Br(2)) obtained using ultraviolet fundamental wavelengths between 280 and 312.5 nm and monitoring Br(+) fragments in a time-of-flight mass spectrometer are found to differ dramatically from those reported in the literature by detecting C(2)H(2)(+). Laser power plots suggest that the initial excitation process is (2+1) REMPI, which accesses parent excited states between 156.25 and 140.84 nm. Unlike the spectra obtained by monitoring C(2)H(2)(+), the spectra obtained by monitoring Br(+) appear to be identical regardless of which parent isomer (cis or trans) is excited. Based on energetics, it is proposed that Br(+) ions are formed by excitation and fragmentation of a ground-state 2-bromovinyl radical intermediate (CHBr=CH.) generated by the rapid excited-state dissociation of the parent molecules. Density-functional theory calculations using the hybrid Perdew-Burke-Ernzerhof (PBE1PBE) functional and the 6-311++G(3df,3pd) basis set confirm that the barrier to isomerization for the 2-bromovinyl radicals formed from the cis- and trans-1,2-dibromoethylenes is low, which explains why the resultant REMPI spectra cannot be distinguished based on their isomeric origin. Electronic spectra calculated for the 2-bromovinyl radical using the long-range-corrected hybrid PBE functional (LC-omegaPBE) are in qualitative agreement with experimental results.

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Elimination mechanisms of Br2+ and Br+ in photodissociation of 1,1- and 1,2-dibromoethylenes using velocity imaging technique

Lee

Chao

et al. 2011

The Journal of Chemical Physics

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Elimination pathways of the Br(2)(+) and Br(+) ionic fragments in photodissociation of 1,2- and 1,1-dibromoethylenes (C(2)H(2)Br(2)) at 233 nm are investigated using time-of-flight mass spectrometer equipped with velocity ion imaging. The Br(2)(+) fragments are verified not to stem from ionization of neutral Br(2), that is a dissociation channel of dibromoethylenes reported previously. Instead, they are produced from dissociative ionization of dibromoethylene isomers. That is, C(2)H(2)Br(2) is first ionized by absorbing two photons, followed by the dissociation scheme, C(2)H(2)Br(2)(+) + hv→Br(2)(+) + C(2)H(2). 1,2-C(2)H(2)Br(2) gives rise to a bright Br(2)(+) image with anisotropy parameter of -0.5 ± 0.1; the fragment may recoil at an angle of ∼66° with respect to the C=C bond axis. However, this channel is relatively slow in 1,1-C(2)H(2)Br(2) such that a weak Br(2)(+) image is acquired with anisotropy parameter equal to zero, indicative of an isotropic recoil fragment distribution. It is more complicated to understand the formation mechanisms of Br(+). Three routes are proposed for dissociation of 1,2-C(2)H(2)Br(2), including (a) ionization of Br that is eliminated from C(2)H(2)Br(2) by absorbing one photon, (b) dissociation from C(2)H(2)Br(2)(+) by absorbing two more photons, and (c) dissociation of Br(2)(+). Each pathway requires four photons to release one Br(+), in contrast to the Br(2)(+) formation that involves a three-photon process. As for 1,1-C(2)H(2)Br(2), the first two pathways are the same, but the third one is too weak to be detected.

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Rydberg spectra of trans-1,2-dibromoethylene

Cited by 4 publications

References 31 publications

Introducing many-body physics using atomic spectroscopy

Introducing many-body physics using atomic spectroscopy

Photodissociation of the geometric isomers of 1,2-dibromoethylene

Elimination mechanisms of Br2+ and Br+ in photodissociation of 1,1- and 1,2-dibromoethylenes using velocity imaging technique

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