Experimental and theoretical studies of the N2++O2 reaction

Michael J. Frost

Research output: Contribution to journalArticle

Abstract

A technique by which ions are formed by resonance-enhanced multiphoton ionisation (REMPI) and detected by laser-induced fluorescence (LIF) has been employed to measure the kinetics of the N2++O2 reaction over the pressure range 5-484 Torr He at 296 K. Within this pressure range, measured rate constants for the reaction are found to increase by a factor of ~2. It is well-established that the reaction proceeds predominantly by charge transfer at low pressure (<1 Torr). At higher pressures, the increase in rate constant for the reaction implies an increasing importance of the stabilisation of [N2·O2] + complexes. However, the observed dependence of rate constants on pressure provides good evidence that charge transfer also proceeds via [N 2·O2]+ complexes and that the contribution of charge transfer to the observed rate constant is pressure-dependendent. Extensive electronic structure calculations conducted at the QCISD/6-311G(d) level are presented and provide a framework to rationalise the experimental results.

Original languageEnglish
Pages (from-to)3169-3173
Number of pages5
JournalPhysical Chemistry Chemical Physics
Volume5
Issue number15
DOIs
Publication statusPublished - 1 Aug 2003

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Rate constants
Charge transfer
Ionization
Electronic structure
Stabilization
Fluorescence
Ions
Kinetics
Lasers

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Frost, Michael J. / Experimental and theoretical studies of the N2++O2 reaction. In: Physical Chemistry Chemical Physics. 2003 ; Vol. 5, No. 15. pp. 3169-3173.
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Experimental and theoretical studies of the N2++O2 reaction. / Frost, Michael J.

In: Physical Chemistry Chemical Physics, Vol. 5, No. 15, 01.08.2003, p. 3169-3173.

Research output: Contribution to journalArticle

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