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

We report the observation of chemical reactions in gas-phase Rh(n)(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.

[1]  D. Harding,et al.  Platinum group metal clusters: from gas-phase structures and reactivities towards model catalysts. , 2014, Chemistry.

[2]  M. Beyer,et al.  Collisional activation of N2O decomposition and CO oxidation reactions on isolated rhodium clusters. , 2013, The journal of physical chemistry. A.

[3]  J. Klassen,et al.  Mapping Protein–Ligand Interactions in the Gas Phase Using a Functional Group Replacement Strategy. Comparison of CID and BIRD Activation Methods , 2013, Journal of The American Society for Mass Spectrometry.

[4]  M. Beyer,et al.  Reactions of M(+)(H2O)n, n < 40, M = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, with D2O reveal water activation in Mn(+)(H2O)n. , 2012, The journal of physical chemistry. A.

[5]  T. D. Fridgen,et al.  Water binding energies of [Pb(amino acid-H)H2O]+ complexes determined by blackbody infrared radiative dissociation. , 2012, Physical chemistry chemical physics : PCCP.

[6]  S. M. Lang,et al.  Gas phase metal cluster model systems for heterogeneous catalysis. , 2012, Physical chemistry chemical physics : PCCP.

[7]  A. Yamada,et al.  Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters. , 2012, Physical chemistry chemical physics : PCCP.

[8]  D. Harding,et al.  Effects of Coadsorbed Oxygen on the Infrared Driven Decomposition of N2O on Isolated Rh5+ Clusters , 2011 .

[9]  Hujun Xie,et al.  Nitric oxide adsorption and reduction reaction mechanism on the Rh7(+) cluster: a density functional theory study. , 2011, The journal of physical chemistry. A.

[10]  J. Klassen,et al.  Blackbody Infrared Radiative Dissociation of Protonated Oligosaccharides , 2011, Journal of the American Society for Mass Spectrometry.

[11]  T. Walsh,et al.  Infrared-induced reactivity of N2O on small gas-phase rhodium clusters. , 2011, The journal of physical chemistry. A.

[12]  T. Walsh,et al.  Infrared induced reactivity on the surface of isolated size-selected clusters: dissociation of N2O on rhodium clusters. , 2010, Journal of the American Chemical Society.

[13]  M. Beyer,et al.  A novel design of a temperature-controlled FT-ICR cell for low-temperature black-body infrared radiative dissociation (BIRD) studies of hydrated ions , 2009 .

[14]  T. Walsh,et al.  Oxides of small Rhodium clusters: Theoretical investigation of experimental reactivities. , 2008, The Journal of chemical physics.

[15]  M. F. Bush,et al.  Reactivity and infrared spectroscopy of gaseous hydrated trivalent metal ions. , 2008, Journal of the American Chemical Society.

[16]  T. Walsh,et al.  Dramatic size effects and evidence of structural isomers in the reactions of rhodium clusters, Rhn+/-, with nitrous oxide. , 2007, Physical chemistry chemical physics : PCCP.

[17]  T. Walsh,et al.  Structural isomers and reactivity for Rh6 and Rh6+. , 2006, The journal of physical chemistry. B.

[18]  D. P. Woodruff,et al.  Nitric oxide decomposition on small rhodium clusters, Rh(n)+/-. , 2006, The journal of physical chemistry. A.

[19]  E. Uggerud,et al.  C-H activation of alkanes on Rh+ n (n=1-30) clusters: size effects on dehydrogenation. , 2005, The Journal of chemical physics.

[20]  J. Klassen,et al.  Blackbody infrared radiative dissociation of nonspecific protein-carbohydrate complexes produced by nanoelectrospray ionization: The nature of the noncovalent interactions , 2005, Journal of the American Society for Mass Spectrometry.

[21]  D. P. Woodruff,et al.  Reactions of nitric oxide on Rh6+ clusters: abundant chemistry and evidence of structural isomers. , 2005, Physical chemistry chemical physics : PCCP.

[22]  R. O'hair,et al.  Gas Phase Ion Chemistry of Transition Metal Clusters: Production, Reactivity, and Catalysis , 2004 .

[23]  R. Dunbar.  BIRD (blackbody infrared radiative dissociation): evolution, principles, and applications. , 2004, Mass spectrometry reviews.

[24]  M. Beyer,et al.  Black Body Fragmentation of Cationic Ammonia Clusters , 2001 .

[25]  P. Armentrout,et al.  Reactions and thermochemistry of small transition metal cluster ions. , 2001, Annual review of physical chemistry.

[26]  M. Knickelbein.  Reactions of transition metal clusters with small molecules. , 1999, Annual review of physical chemistry.

[27]  R. A. Jockusch,et al.  Binding energies of protonated betaine complexes: a probe of zwitterion structure in the gas phase. , 1998, Journal of the American Chemical Society.

[28]  T. Mcmahon,et al.  Activation of Unimolecular Reactions by Ambient Blackbody Radiation , 1998 .

[29]  P. Schnier,et al.  Effects of charge state on fragmentation pathways, dynamics, and activation energies of ubiquitin ions measured by blackbody infrared radiative dissociation. , 1997, Analytical chemistry.

[30]  P. Schnier,et al.  Unimolecular reaction kinetics in the high-pressure limit without collisions. , 1996, Journal of the American Chemical Society.

[31]  V. Bondybey,et al.  Protonated water clusters and their black body radiation induced fragmentation , 1996 .

[32]  R. Dunbar.  Kinetics of thermal unimolecular dissociation by ambient infrared radiation , 1994 .

[33]  T. Mcmahon,et al.  Spontaneous Unimolecular Dissociation of Small Cluster Ions, (H3O+)Ln and Cl-(H2O)n (n = 2-4), under Fourier Transform Ion Cyclotron Resonance Conditions , 1994 .

[34]  V. Bondybey,et al.  Gas‐Phase Reactivity of Sulphur Cluster Cations and Anions by FT‐ICR Investigations , 1992 .