Search results for "matrix isolation"

Matrix isolation and quantum chemical studies on the H2O2–SO2complex

2004

Complexation and photochemical reactions of hydrogen peroxide and sulfur dioxide have been studied in solid Ar, Kr and Xe. Complexes between H2O2 and SO2 are characterized using Fourier transform infrared spectroscopy and ab initio calculations. In solid Ar, the H2O2–SO2 complex absorptions are found at wavenumbers of 3572.8, 3518.7, 3511.2, 3504.3, 1340.3, 1280.2 and 1149.9 cm−1. In Kr and Xe matrices, the bonded OH stretching frequencies deviate from the values in Ar, and we propose that the matrix surrounding influences the structure of the H2O2–SO2 complex. UV photolysis of the H2O2–SO2 was also studied in solid Ar, Kr and Xe. This photolysis produces mainly a complex between sulfur tri…

Isolating reactive metal-based species in Metal-Organic Frameworks - viable strategies and opportunities.

2021

Structural insight into reactive species can be achieved via strategies such as matrix isolation in frozen glasses, whereby species are kinetically trapped, or by confinement within the cavities of host molecules. More recently, Metal–Organic Frameworks (MOFs) have been used as molecular scaffolds to isolate reactive metal-based species within their ordered pore networks. These studies have uncovered new reactivity, allowed observation of novel metal-based complexes and clusters, and elucidated the nature of metal-centred reactions responsible for catalysis. This perspective considers strategies by which metal species can be introduced into MOFs and highlights some of the advantages and lim…

Matrix-isolation and ab initio study of the complex between formic acid and xenon

2012

Abstract We report on the identification of the complexes of formic acid (FA) and Xe in an argon matrix. The geometries, interaction energies, reaction barriers, and vibrational spectra of the FA⋯Xe complexes are calculated at the MP2 level of theory. The calculations reveal four structures for the trans-FA⋯Xe complex and four structures for the cis-FA⋯Xe complex. In the experiments, two structures of the trans-FA⋯Xe complex are observed after deposition of FA/Xe/Ar matrices, with and without OH⋯Xe interaction (H-bonded and non-H-bonded structures). The cis-FA⋯Xe complex was synthesized by vibrational excitation of the non-H-bonded trans-FA⋯Xe complex. The non-H-bonded and H-bonded structur…

2019

Structural changes of glycolic acid (GA) complex with nitrogen induced by selective overtone excitation of the νOH mode were followed in argon matrices using FTIR spectroscopy. For the most stable SSC1 complex present in different trapping sites directly upon deposition site, selective changes in the νOH region were achieved upon near-infrared irradiation. Simultaneously, new conformers of the GA…N2 complex were formed, giving rise to several sets of bands in the νOH and νC=O regions of the spectra. Both position and intensity of new absorptions appeared to be highly sensitive on the wavelength of radiation used, as well as on the annealing of the matrix. Based on theoretical calculations a…

The characterization of molecular alkaly metal azides

2006

Matrix isolation infrared (IR) studies have been carried out on the vaporisation of the alkali-metal azides MN(3) (M = Na, K, Rb and Cs). The results show that under high vacuum conditions, molecular KN(3), RbN(3) and CsN(3) are present as stable high-temperature vapour species, together with variable amounts of nitrogen gas and the corresponding metal atoms. The characterisation of these molecular azides is supported by ab initio molecular orbital calculations and density functional theory (DFT) calculations, and for CsN(3) in particular, by the detection of the isotopomers CS((14)N(15)N(14)N) and Cs((15)N(14)N(14)N). The IR spectra are assigned to a "side-on" (C(2v)) structure by comparis…

Matrix isolation studies and DFT calculations on molecular alkali metal bromates

2009

DFT and MP2 calculations have been carried out on a series of molecular alkali metal bromates MBrO3 (M = Na, K, Rb, Cs), and the results compared with matrix isolation IR studies on the vaporisation of the solid salts. For M = Na, K or Rb, no ternary molecular species were detected in the low temperature matrix, but vaporisation of solid caesium bromate at 730 K resulted in the formation of molecular CsBrO3, which was identified as having a C3v structure involving tridentate coordination. Additionally, the DFT and MP2 calculations provide estimates of the molecular parameters for all four MBrO3 species, and for the related MXO3 species CsClO3 and CsIO3. The proven stability of MBrO3 molecul…

HC-SCR of NOx over Ag/alumina: a combination of heterogeneous and homogeneous radical reactions?

2005

Matrix isolation combined with EPR and FT-IR technique at low temperature has been used to study the gas phase species involved in HC-SCR over a highly active Ag/alumina catalyst. A combination of heterogeneous and homogeneous (radical) reactions is proposed to take place over a Ag/alumina catalyst during HC-SCR. Radicals of low molecular weight were trapped in a growing argon matrix behind the Ag/alumina catalyst. In the same matrix, cyanogen isocyanate was detected and is suggested to be a key intermediate for the formation of amines and ammonia via the hydrolysis of isocyanate species.

Raman spectroscopy of acetic acid monomer and dimers isolated in solid argon

2011

Acetic acid (AA) monomer and its dimers were studied by means of Raman spectroscopy combined with the matrix isolation technique. All fundamental bands of CH3COOH monomer were identified, including the CH3 torsional mode. Additionally, three overtone or combination modes were observed as a result of their enhanced intensities by Fermi resonance (FR). Twenty bands of the cyclic dimer (C2h) were identified and assigned, among which appear all intermolecular modes. Bands due to two different higher energy forms of the dimer were also identified. The experimental assignments are supported by ab initio calculations. Copyright © 2011 John Wiley & Sons, Ltd.

MALDI-TOF characterization of macromonomers

1996

Methacryloyl endfunctionalized oligostyrene macromonomers were characterized by matrix assisted laser desorption ionization/time of flight (MALDI-TOF) spectroscopy and by isocratic and gradient high performance liquid chromatography (HPLC). The molar mass distribution derived by the different techniques coincide for the investigated oligomers. Mixing experiments revealed that the MALDI-TOF peak areas do not necessarily represent the mixing ratio of the components. Combination of gradient HPLC and MALDI-TOF has resolved the chemical composition of the coupling products formed by reaction of the living anion with oxygen.

Spectroscopy of Alkali Atoms in Solid Matrices of Rare Gases: Experimental Results and Theoretical Analysis

2022

We present an experimental and theoretical investigation of the spectroscopy of dilute alkali atoms in a solid matrix of inert gases at cryogenic temperatures, specifically Rubidium atoms in a solid Argon or Neon matrix, and related aspects of the interaction energies between the alkali atoms and the atoms of the solid matrix. The system considered is relevant for matrix isolation spectroscopy, and it is at the basis of a recently proposed detector of cosmological axions, exploiting magnetic-type transitions between Zeeman sublevels of alkali atoms in a magnetic field, tuned to the axion mass, assumed in the meV range. Axions are one of the supposed constituents of the dark matter (DM) of t…