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Generation and high-resolution photoelectron spectroscopy of small organic radicals in cold supersonic expansions

Generation and high-resolution photoelectron spectroscopy of small organic radicals in cold supersonic expansions
Generation and high-resolution photoelectron spectroscopy of small organic radicals in cold supersonic expansions
A general method of generating radicals in cold supersonic expansions in the gas phase is presented. The method relies on excimer laser photolysis of suitable precursor molecules in a thin quartz capillary mounted at the orifice of a pulsed gas nozzle and can easily be combined with vacuum-UV photoionization mass spectrometry and high-resolution photoelectron spectroscopy to study the reactivity and the rovibronic energy level structure of neutral radicals and their ions, as well as to determine highly accurate adiabatic ionization energies. The characteristics of the radical source are described in detail, and its performance is illustrated by mass spectrometric and high-resolution photoelectron spectroscopic investigations of NH2, CH2, CH3, C2H, C2H3, and C2H5. The radical source is not only suitable to produce cold samples (rotational temperature of ca. 30 K) of radicals of moderate reactivity, such as NH2, CH3, or C2H5, but it is also useful to prepare highly reactive radicals (e.g., C2H) for spectroscopic investigations.
selective photodissociation dynamics, high rydberg states, infrared-spectroscopy, photoionization mass, bond-dissociation, ionization-energy, field-ionization, discharge source, cavity ring, spectrum
0018-019X
1152-1166
Willitsch, Stefan
076aaf36-e87c-4054-86d5-8601cc70e620
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Merkt, Frédéric
06a18f24-5f0b-4a45-9925-e152904278e6
Willitsch, Stefan
076aaf36-e87c-4054-86d5-8601cc70e620
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Merkt, Frédéric
06a18f24-5f0b-4a45-9925-e152904278e6

Willitsch, Stefan, Dyke, John M. and Merkt, Frédéric (2003) Generation and high-resolution photoelectron spectroscopy of small organic radicals in cold supersonic expansions. Helvetica Chimica Acta, 86 (4), 1152-1166. (doi:10.1002/hlca.200390100).

Record type: Article

Abstract

A general method of generating radicals in cold supersonic expansions in the gas phase is presented. The method relies on excimer laser photolysis of suitable precursor molecules in a thin quartz capillary mounted at the orifice of a pulsed gas nozzle and can easily be combined with vacuum-UV photoionization mass spectrometry and high-resolution photoelectron spectroscopy to study the reactivity and the rovibronic energy level structure of neutral radicals and their ions, as well as to determine highly accurate adiabatic ionization energies. The characteristics of the radical source are described in detail, and its performance is illustrated by mass spectrometric and high-resolution photoelectron spectroscopic investigations of NH2, CH2, CH3, C2H, C2H3, and C2H5. The radical source is not only suitable to produce cold samples (rotational temperature of ca. 30 K) of radicals of moderate reactivity, such as NH2, CH3, or C2H5, but it is also useful to prepare highly reactive radicals (e.g., C2H) for spectroscopic investigations.

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More information

Published date: 2003
Keywords: selective photodissociation dynamics, high rydberg states, infrared-spectroscopy, photoionization mass, bond-dissociation, ionization-energy, field-ionization, discharge source, cavity ring, spectrum

Identifiers

Local EPrints ID: 20105
URI: http://eprints.soton.ac.uk/id/eprint/20105
ISSN: 0018-019X
PURE UUID: 2eba7ed3-4ae7-44cc-ab46-09863b9878c0
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

Catalogue record

Date deposited: 23 Feb 2006
Last modified: 16 Mar 2024 02:36

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Contributors

Author: Stefan Willitsch
Author: John M. Dyke ORCID iD
Author: Frédéric Merkt

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