10K Ring Electrode Trap - Tandem Mass Spectrometer for Infrared Spectroscopy of Mass Selected Ions

A novel instrumental setup for measuring infrared photodissociation spectra of buffer gas cooled, mass-selected ions is described and tested. It combines a cryogenically cooled, linear radio frequency ion trap with a tandem mass spectrometer, optimally coupling continuous ion sources to pulsed laser experiments. The use of six independently adjustable DC potentials superimposed over the trapping radio frequency field provides control over the ion distribution within, as well as the kinetic energy distribution of the ions extracted from the ion trap. The scheme allows focusing the ions in space and time, such that they can be optimally irradiated by a pulsed, widely tunable infrared photodissociation laser. Ion intensities are monitored with a time-of-flight mass spectrometer mounted orthogonally to the ion trap axis

Negative ion formation in potassium–nitromethane collisions

Ion-pair formation in gaseous nitromethane (CH3NO2) induced by electron transfer has been studied by investigating the products of collisions between fast potassium atoms and nitromethane molecules using a crossed molecular-beam technique. The negative ions formed in such collisions were analysed using time-of-flight mass spectroscopy. The six most dominant product anions are NO2?, O?, CH3NO2?, OH?, CH2NO2? and CNO?. By using nitromethane-d3 (CD3NO2), we found that previous mass 17 amu assignment to O? delayed fragment, is in the present experiment may be unambiguously assigned to OH?. The formation of CH2NO2? may be explained in terms of dissociative electron attachment to highly vibrationally excited molecules

Surface-Enhanced Nitrate Photolysis on Ice

Heterogeneous nitrates photolysis is the trigger for many chemical processes occurring in the polar boundary layer and is widely believed to occur in a quasi-liquid layer (QLL) at the surface of ice. The dipole forbidden character of the electronic transition relevant to boundary layer atmospheric chemistry and the small photolysis/photoproducts quantum yields in ice (and in water) may confer a significant enhancement and interfacial specificity to this important photochemical reaction at the surface of ice. Using amorphous solid water films at cryogenic temperatures as models for the disordered interstitial air/ice interface within the snowpack suppresses the diffusive uptake kinetics thereby prolonging the residence time of nitrate anions at the surface of ice. This approach allows their slow heterogeneous photolysis kinetics to be studied providing the first direct evidence that nitrates adsorbed onto the first molecular layer at the surface of ice are photolyzed more effectively than those dissolved within the bulk. Vibrational spectroscopy allows the ~3-fold enhancement in photolysis rates to be correlated with the nitrates’ distorted intramolecular geometry thereby hinting at the role played by the greater chemical heterogeneity in their solvation environment at the surface of ice than in the bulk. A simple 1D kinetic model suggests 1-that a 3(6)-fold enhancement in photolysis rate for nitrates adsorbed onto the ice surface could increase the photochemical NO[subscript 2] emissions from a 5(8) nm thick photochemically active interfacial layer by 30%(60)%, and 2-that 25%(40%) of the NO[subscript 2] photochemical emissions to the snowpack interstitial air are released from the top-most molecularly thin surface layer on ice. These findings may provide a new paradigm for heterogeneous (photo)chemistry at temperatures below those required for a QLL to form at the ice surface

Six-Coordinate Nitrito and Nitrato Complexes of Manganese Porphyrin

Reaction of small increments of NO2 gas with sublimed amorphous layers of Mn(II)(TPP) (TPP = meso-tetra-phenylporphyrinato dianion) in a vacuum cryostat leads to formation of the 5-coordinate monodentate nitrato complex Mn(III)(TPP)(η(1)-ONO2) (II). This transformation proceeds through the two distinct steps with initial formation of the five coordinate O-nitrito complex Mn(III)(TPP)(η(1)-ONO) (I) as demonstrated by the electronic absorption spectra and by FTIR spectra using differently labeled nitrogen dioxide. A plausible mechanism for the second stage of reaction is offered based on the spectral changes observed upon subsequent interaction of (15)NO2 and NO2 with the layered Mn(TPP). Low-temperature interaction of I and II with the vapors of various ligands L (L = O-, S-, and N-donors) leads to formation of the 6-coordinate O-nitrito Mn(III)(TPP)(L)(η(1)-ONO) and monodentate nitrato Mn(III)(TPP)(L)(η(1)-ONO2) complexes, respectively. Formation of the 6-coordinate O-nitrito complex is accompanied by the shifts of the ν(N═O) band to lower frequency and of the ν(N-O) band to higher frequency. The frequency difference between these bands Δν = ν(N═O) - ν(N-O) is a function of L and is smaller for the stronger bases. Reaction of excess NH3 with I leads to formation of Mn(TPP)(NH3)(η(1)-ONO) and of the cation [Mn(TPP)(NH3)2](+) plus ionic nitrite. The nitrito complexes are relatively unstable, but several of the nitrato species can be observed in the solid state at room temperature. For example, the tetrahydrofuran complex Mn(TPP)(THF)(η(1)-ONO2) is stable in the presence of THF vapors (∼5 mm), but it loses this ligand upon high vacuum pumping at RT. When L = dimethylsulfide (DMS), the nitrato complex is stable only to ∼-30 °C. Reactions of II with the N-donor ligands NH3, pyridine, or 1-methylimidazole are more complex. With these ligands, the nitrato complexes Mn(III)(TPP)(L)(η(1)-ONO2) and the cationic complexes [Mn(TPP)(L)2](+) coexist in the layer at room temperature, the latter formed as a result of NO3(-) displacement when L is in excess

Vibrational spectra of small silicon monoxide cluster cations measured by infrared multiple photon dissociation spectroscopy

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Vibrational signatures of hydrogen bonding in the protonated ammonia clusters NH4+(NH3)(1-4)

The gas phase vibrational spectroscopy of the protonated ammonia dimer N2H7+, a prototypical system for strong hydrogen bonding, is studied in the spectral region from 330 to 1650 cm(-1) by combining infrared multiple photon dissociation and multidimensional quantum mechanical simulations. The fundamental transition of the antisymmetric proton stretching vibration is observed at 374 cm(-1) and assigned on the basis of a six-dimensional model Hamiltonian, which predicts this transition at 471 cm(-1). Photodissociation spectra of the larger protonated ammonia clusters NH4+(NH3)(n) with n=2-4 are also reported for the range from 1050 to 1575 cm(-1). The main absorption features can be assigned within the harmonic approximation, supporting earlier evidence that hydrogen bonding in these clusters is considerably weaker than for n=1