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Chemical Reactivity on Gas‐Phase Metal Clusters Driven by Blackbody Infrared Radiation
Author(s) -
Parry Imogen S.,
Kartouzian Aras,
Hamilton Suzanne M.,
Balaj O. Petru,
Beyer Martin K.,
Mackenzie Stuart R.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201409483
Subject(s) - fourier transform ion cyclotron resonance , black body radiation , infrared , analytical chemistry (journal) , chemistry , absorption (acoustics) , infrared spectroscopy , fourier transform infrared spectroscopy , mass spectrometry , photochemistry , materials science , radiation , physics , organic chemistry , optics , chromatography , composite material
We report the observation of chemical reactions in gas‐phase Rh n (N 2 O) 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 N 2 O moieties promotes a small fraction of the cluster distribution sufficiently to drive the N 2 O decomposition reaction, leading to the production of cluster oxides and the release of molecular nitrogen. N 2 O 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.