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Title: Effusive molecular beam-sampled Knudsen flow reactor coupled to vacuum ultraviolet single photon ionization mass spectrometry using an external free radical source

A new apparatus using vacuum ultraviolet single photon ionization mass spectrometry (VUV SPIMS) of an effusive molecular beam emanating from a Knudsen flow reactor is described. It was designed to study free radical-molecule kinetics over a significant temperature range (300–630 K). Its salient features are: (1) external free radical source, (2) counterpropagating molecular beam and diffuse VUV photon beam meeting in a crossed-beam ion source of a quadrupole mass spectrometer with perpendicular ion extraction, (3) analog detection of the photocurrent of the free radical molecular cation, and (4) possibility of detecting both free radicals and closed shell species in the same apparatus and under identical reaction conditions owing to the presence of photoelectrons generated by the photoelectric effect of the used VUV-photons. The measured thermal molecular beam-to-background ratio was 6.35 ± 0.39 for Ar and 10.86 ± 1.59 for i-C{sub 4}H{sub 10} at 300 K, a factor of 2.52 and 1.50 smaller, respectively, than predicted from basic gas-dynamic considerations. Operating parameters as well as the performance of key elements of the instrument are presented and discussed. Coupled to an external free radical source a steady-state specific exit flow of 1.6 × 10{sup 11} and 5.0 × 10{sup 11} molecule s{supmore » −1} cm{sup −3} of C{sub 2}H{sub 5}{sup •} (ethyl) and t-C{sub 4}H{sub 9}{sup •} (t-butyl) free radicals have been detected using VUV SPIMS at their molecular ion m/z 29 and 57, respectively, at 300 K.« less
Authors:
;  [1]
  1. Laboratory of Atmospheric Chemistry (LAC), Paul Scherrer Institute (PSI), CH-5232 Villigen PSI (Switzerland)
Publication Date:
OSTI Identifier:
22220329
Resource Type:
Journal Article
Resource Relation:
Journal Name: Review of Scientific Instruments; Journal Volume: 84; Journal Issue: 11; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY; 2-METHYLPROPANE; BUTANE; CATIONS; COLLIDING BEAMS; EQUIPMENT; FAR ULTRAVIOLET RADIATION; HYDROGEN 4; KNUDSEN FLOW; MASS SPECTROSCOPY; MOLECULAR BEAMS; MOLECULAR IONS; PHOTOIONIZATION; PHOTON BEAMS; PHOTONS; RADICALS; REACTION KINETICS