An aromatic noble-gas hydride : C6H5CCXeH

We report on the aromatic noble-gas hydride, C6H5CCXeH, identified in a xenon matrix using infrared spectroscopy and extensive quantum chemical calculations. This molecule is prepared by 250-nm photolysis of phenylacetylene (C6H5CCH) isolated in a xenon matrix and subsequent thermal mobilization of hydrogen atoms at about 40 K. The characteristic H-Xe stretching mode of C6H5CCXeH is observed at about 1500 cm(-1), and a number of other fundamentals also appear in the experimental spectra. The assignment is supported by deuteration experiments providing predictable shifts of the vibrational frequencies. The experimental and calculated spectra are in a good agreement. C6H5CCXeH is computationally lower in energy than the C6H5CC + Xe + H fragments by about 0.60 eV at the M06-2X/aug-cc-pVTZ-PP level of theory, which allows its formation at low temperatures. C6H5CCXeH is the first aromatic noble-gas hydride and the first halogen-free aromatic noble-gas compound.Peer reviewe

Thermal decomposition of the HXeCl center dot center dot center dot H2O complex in solid xenon : Experimental characterization of the two-body decomposition channel

The thermal decomposition process of HXeCl···H2O in solid Xe is studied, and HCl···H2O is identified as a decomposition product. The production is due to the two-body (2B) decomposition of HXeCl moiety, in agreement with theoretical predictions. Two types of 2B decomposition paths are predicted: catalytic and unimolecular 2B decompositions, where water molecule plays different roles. In an experiment to selectively produce HXeCl···D2O, only HCl···D2O is observed as a thermal decomposition product, indicating the occurrence of unimolecular 2B decomposition, where water molecule serves as a spectator. The activation energy for this decomposition process is experimentally determined to be 15 kJ mol−1.The thermal decomposition process of HXeCl center dot center dot center dot H2O in solid Xe is studied, and HCl center dot center dot center dot H2O is identified as a decomposition product. The production is due to the two-body (2B) decomposition of HXeCl moiety, in agreement with theoretical predictions. Two types of 2B decomposition paths are predicted: catalytic and unimolecular 2B decompositions, where water molecule plays different roles. In an experiment to selectively produce HXeCl center dot center dot center dot D2O, only HCl center dot center dot center dot D2O is observed as a thermal decomposition product, indicating the occurrence of unimolecular 2B decomposition, where water molecule serves as a spectator. The activation energy for this decomposition process is experimentally determined to be 15 kJ mol(-1).Peer reviewe

Photonic Properties of Silicon-Based Materials

Non peer reviewe

Silicon Nanoscale Materials : From Theoretical Simulations to Photonic Applications

Peer reviewe

Surface-Enhanced Raman Scattering of Silicon Nanocrystals in a Silica Film

Surface-enhanced Raman scattering (SERS) is an intriguing effect, efficiency of which depends on many factors and whose applicability to a given system is not obvious before the experiment. The motivation of the present work is to demonstrate the SERS effect on silicon nanocrystals (Si-nc) embedded in silica, the material of high technological importance. Using the Ag overlayer method, we have found the SERS effect for this material. The best result is obtained for Ag layers of a weight thickness of 12 nm, whose surface plasmons are in a resonance with the laser wavelength (488 nm). The enhancement obtained for the Raman signal from 3-4-nm Si-nc in a 40-nm SiOx film is above 100. The SERS effect is about twice stronger for ultra-small Si-nc (similar to 1 nm) and/or disordered silicon compared to Si-nc with sizes of 3-4 nm. The SERS measurements with an Ag overlayer allow detecting silicon crystallization for ultrathin SiOx films and/or for very low Si excess and suppress the Raman signal from the substrate and the photoluminescence of the film.Peer reviewe

Optical and Structural Properties of Si Nanocrystals in SiO2 Films

Optical and structural properties of Si nanocrystals (Si-nc) in silica films are described. For the SiOx (x <2) films annealed above 1000 degrees C, the Raman signal of Si-nc and the absorption coefficient are proportional to the amount of elemental Si detected by X-ray photoelectron spectroscopy. A good agreement is found between the measured refractive index and the value estimated by using the effective-medium approximation. The extinction coefficient of elemental Si is found to be between the values of crystalline and amorphous Si. Thermal annealing increases the degree of Si crystallization; however, the crystallization and the Si-SiO2 phase separation are not complete after annealing at 1200 degrees C. The 1.5-eV PL quantum yield increases as the amount of elemental Si decreases; thus, this PL is probably not directly from Si-nc responsible for absorption and detected by Raman spectroscopy. Continuous-wave laser light can produce very high temperatures in the free-standing films, which changes their structural and optical properties. For relatively large laser spots, the center of the laser-annealed area is very transparent and consists of amorphous SiO2. Large Si-nc (up to ~300 nm in diameter) are observed in the ring around the central region. These Si-nc lead to high absorption and they are typically under compressive stress, which is connected with their formation from the liquid phase. By using strongly focused laser beams, the structural changes in the free-standing films can be made in submicron areas.Peer reviewe

Reaction of atomic hydrogen with formic acid

Peer reviewe

Spectroscopic characterization of the complex of vinyl radical and carbon dioxide : Matrix isolation and ab initio study

We report on the preparation and vibrational characterization of the C2H3 center dot center dot center dot CO2 complex, the first example of a stable intermolecular complex involving vinyl radicals. This complex was prepared in Ar and Kr matrices using UV photolysis of propiolic acid (HC3OOH) and subsequent thermal mobilization of H atoms. This preparation procedure provides vinyl radicals formed exclusively as a complex with CO2, without the presence of either CO2 or C2H3 monomers. The absorption bands corresponding to the nu(5)(C2H3), nu(7)(C2H3), nu(8)(C2H3), nu(2)(CO2), and nu(3)(CO2) modes of the C2H3 center dot center dot center dot CO2 complex were detected experimentally. The calculations at the UCCSD(T)/L2a level of theory predict two structures of the C2H3 center dot center dot center dot CO2 complex with C-s and C-1 symmetries and interaction energies of -1.92 and -5.19 kJ mol(-1). The harmonic vibrational frequencies of these structures were calculated at the same level of theory. The structural assignment of the experimental species is not straightforward because of rather small complexation-induced shifts and matrix-site splitting of the bands (for both complex and monomers). We conclude that the C-1 structure is the most probable candidate for the experimental C2H3 center dot center dot center dot O-2 complex based on the significant splitting of the bending vibration of CO2 and on the energetic and structural considerations. Published by AIP Publishing.Peer reviewe

Matrix-isolation and computational study of the HKrCCH center dot center dot center dot HCCH complex

The HKrCCH center dot center dot center dot HCCH complex is identified in a Kr matrix with the H-Kr stretching bands at 1316.5 and 1305 cm(-1). The monomer-to-complex shift of the H-Kr stretching mode is about +60 cm(-1), which is significantly larger than that reported previously for the HXeCCH center dot center dot center dot HCCH complex in a Xe matrix (about +25 cm(-1)). The HKrCCH center dot center dot center dot HCCH complex in a Kr matrix is formed at similar to 40 K via the attachment of mobile acetylene molecules to the HKrCCH monomers formed at somewhat lower annealing temperatures upon thermally-induced mobility of H atoms (similar to 30 K). The same mechanism was previously proposed for the formation of the HXeCCH center dot center dot center dot HCCH complex in a Xe matrix. The assignment of the HKrCCH center dot center dot center dot HCCH complex is fully supported by the quantum chemical calculations. The experimental shift of the H-Kr stretching mode is comparable with the computational predictions (+46.6, +66.0, and +83.2 cm(-1) at the B3LYP, MP2, and CCSD(T) levels of theory, respectively), which are also bigger that the calculated shift in the HXeCCH center dot center dot center dot HCCH complex. These results confirm that the complexation effect is bigger for less stable noble-gas hydrides.Peer reviewe