Modelling the Dissociation Dynamics and Threshold Photoelectron Spectra of Small Halogenated Molecules

Harvey, Jonelle

doi:10.1007/978-3-319-02976-4

Springer Theses

2014

DOI: 10.1007/978-3-319-02976-4

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Modelling the Dissociation Dynamics and Threshold Photoelectron Spectra of Small Halogenated Molecules

Jonelle Harvey¹

Abstract: The two experimental aspects of the imagining photoelectron photoion coincidence (iPEPICO) apparatus which is stationed at the VUV Beamline at the Swiss Light Source, a synchrotron source, have been used to investigate the fundamental properties of small molecules in the gas phase.

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2017

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Coincident velocity map image reconstruction illustrated by the single-photon valence photoionisation of CF₃SF₅

Bodi

Hemberger

Tuckett

2017

Phys. Chem. Chem. Phys.

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Velocity map imaging offers high energy resolution and collection efficiency of the steady flux of photoelectrons and ions in continuous photoionisation experiments. In this proof-of-principle work, we show by the photoionisation of trifluoromethyl sulphur pentafluoride, CFSF, that the four-dimensional problem of reconstructing coincident velocity map images of electrons and ions of certain mass can be addressed by separating the energy distribution from the angular anisotropy. The energy spectrum is predominantly determined by the radial distribution of the image, whereas laboratory frame angular anisotropies are revealed based on the radial distribution of the image multiplied with a 2nd-degree Legendre polynomial. The reconstruction yields the energy correlation between the photoion and the photoelectron characteristic of the photoelectron spectrum and the kinetic energy release. The angular anisotropy β-parameter maps of the photoelectrons and photoions are also obtained as 2D functions of the electron and ion kinetic energies. For photoionisation of CFSF, the energy correlation reveals suprastatistical kinetic energy release (KER) in CF production in the ground cationic X[combining tilde] state, but statistical KER in the excited Ã and B[combining tilde] state bands. Although the photoelectron distribution is isotropic, the photoion anisotropy in the energy range of the X[combining tilde] state speaks for prompt dissociation after preferential ionisation of CFSF molecules aligned with the polarisation vector of the synchrotron radiation. The angular dependence of the photoionisation cross section is confirmed by ab initio calculations for vertical ionisation.

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Coincident velocity map image reconstruction illustrated by the single-photon valence photoionisation of CF₃SF₅

Bodi

Hemberger

Tuckett

2017

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

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Modelling the Dissociation Dynamics and Threshold Photoelectron Spectra of Small Halogenated Molecules

Abstract: The two experimental aspects of the imagining photoelectron photoion coincidence (iPEPICO) apparatus which is stationed at the VUV Beamline at the Swiss Light Source, a synchrotron source, have been used to investigate the fundamental properties of small molecules in the gas phase.

Cited by 1 publication

References 6 publications

Coincident velocity map image reconstruction illustrated by the single-photon valence photoionisation of CF₃SF₅

Coincident velocity map image reconstruction illustrated by the single-photon valence photoionisation of CF₃SF₅

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Modelling the Dissociation Dynamics and Threshold Photoelectron Spectra of Small Halogenated Molecules

Abstract: The two experimental aspects of the imagining photoelectron photoion coincidence (iPEPICO) apparatus which is stationed at the VUV Beamline at the Swiss Light Source, a synchrotron source, have been used to investigate the fundamental properties of small molecules in the gas phase.

Cited by 1 publication

References 6 publications

Coincident velocity map image reconstruction illustrated by the single-photon valence photoionisation of CF3SF5

Coincident velocity map image reconstruction illustrated by the single-photon valence photoionisation of CF3SF5

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Coincident velocity map image reconstruction illustrated by the single-photon valence photoionisation of CF₃SF₅

Coincident velocity map image reconstruction illustrated by the single-photon valence photoionisation of CF₃SF₅