Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation

We report the observation of chemical reactions in gas-phase Rhn(N2O)m + complexes driven by absorption of blackbody radiation. The experiments are performed under collision-free conditions in a Fourier transform ion cyclotron resonance mass spectrometer. Mid-infrared absorption by the molecularly a...

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Huvudupphovsmän: Parry, I, Kartouzian, A, Hamilton, S, Balaj, O, Beyer, M, Mackenzie, S
Materialtyp: Journal article
Publicerad: Wiley-VCH 2015
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author Parry, I
Kartouzian, A
Hamilton, S
Balaj, O
Beyer, M
Beyer, M
Mackenzie, S
author_facet Parry, I
Kartouzian, A
Hamilton, S
Balaj, O
Beyer, M
Beyer, M
Mackenzie, S
author_sort Parry, I
collection OXFORD
description We report the observation of chemical reactions in gas-phase Rhn(N2O)m + complexes driven by absorption of blackbody radiation. The experiments are performed under collision-free conditions in a Fourier transform ion cyclotron resonance mass spectrometer. Mid-infrared absorption by the molecularly adsorbed N2O moieties promotes a small fraction of the cluster distribution sufficiently to drive the N2O decomposition reaction, leading to the production of cluster oxides and the release of molecular nitrogen. N2O decomposition competes with molecular desorption and the branching ratios for the two processes show marked size effects, reflecting variations in the relative barriers. The rate of decay is shown to scale approximately linearly with the number of infrared chromophores. The experimental findings are interpreted in terms of calculated infrared absorption rates assuming a sudden-death limit.
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spelling oxford-uuid:5ad716c3-edc9-4be9-9a2c-d8acd0606d782022-03-26T17:18:19ZChemical reactivity on gas-phase metal clusters driven by blackbody infrared radiationJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:5ad716c3-edc9-4be9-9a2c-d8acd0606d78Symplectic Elements at OxfordWiley-VCH2015Parry, IKartouzian, AHamilton, SBalaj, OBeyer, MBeyer, MMackenzie, SWe report the observation of chemical reactions in gas-phase Rhn(N2O)m + complexes driven by absorption of blackbody radiation. The experiments are performed under collision-free conditions in a Fourier transform ion cyclotron resonance mass spectrometer. Mid-infrared absorption by the molecularly adsorbed N2O moieties promotes a small fraction of the cluster distribution sufficiently to drive the N2O decomposition reaction, leading to the production of cluster oxides and the release of molecular nitrogen. N2O decomposition competes with molecular desorption and the branching ratios for the two processes show marked size effects, reflecting variations in the relative barriers. The rate of decay is shown to scale approximately linearly with the number of infrared chromophores. The experimental findings are interpreted in terms of calculated infrared absorption rates assuming a sudden-death limit.
spellingShingle Parry, I
Kartouzian, A
Hamilton, S
Balaj, O
Beyer, M
Beyer, M
Mackenzie, S
Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation
title Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation
title_full Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation
title_fullStr Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation
title_full_unstemmed Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation
title_short Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation
title_sort chemical reactivity on gas phase metal clusters driven by blackbody infrared radiation
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AT kartouziana chemicalreactivityongasphasemetalclustersdrivenbyblackbodyinfraredradiation
AT hamiltons chemicalreactivityongasphasemetalclustersdrivenbyblackbodyinfraredradiation
AT balajo chemicalreactivityongasphasemetalclustersdrivenbyblackbodyinfraredradiation
AT beyerm chemicalreactivityongasphasemetalclustersdrivenbyblackbodyinfraredradiation
AT beyerm chemicalreactivityongasphasemetalclustersdrivenbyblackbodyinfraredradiation
AT mackenzies chemicalreactivityongasphasemetalclustersdrivenbyblackbodyinfraredradiation