The Effect of ß-Hydrogens on the Tropospheric Photochemistry of Aldehydes: Norrish Type 1, Triple Fragmentation, and Methylketene Formation from Propanal.

Wavelength and pressure dependent quantum yields (ϕ, QYs) of propanal photolysis have been measured for photolysis wavelengths, λ = 300-330 nm, and buffer gases of 3-10 Torr propanal and 0-757 Torr N2. Following laser photolysis, three photochemical pathways were established, using Fourier transform infrared spectroscopy of the stable end-products. Photolysis is dominated by the Norrish Type 1 reaction, which has been reported previously, but with inconsistent quantum yields. The propanal α-hydrogen leads to a 4-center elimination of H2, as observed in CH3CHO, here leading to methylketene. The presence of hydrogen attached to the ß-carbon allows a new photochemical pathway: concerted triple fragmentation into CO + H2 + C2H4 via a 5-center transition state. Neither of these channels has been reported previously. No evidence for the previously reported C2H6 + CO, C2H4 + H2CO or CH3 + CH2CHO channels, nor for phototautomerization to 1-propenol (CH3CH═CHOH) was found. Modeling of the wavelength, pressure and collision partner dependence of the QYs allows us to reconcile the previous NT1a results and make recommendations for the quantum yields of all three channels under tropospheric conditions. The general impact of ß-hydrogen atoms in the photochemistry of aldehydes is to open up new pathways from cyclic transition states and to reduce the importance of other photolysis or isomerization channels.

Dynamics and quantum yields of H2 + CH2CO as a primary photolysis channel in CH3CHO.

The first experimental observation of the primary photochemical channel of acetaldehyde leading to the formation of ketene (CH2CO) and hydrogen (H2) molecular products is reported. Acetaldehyde (CH3CHO) was photolysed in a molecular beam at 305.6 nm and the resulting H2 product characterized using velocity-map ion (VMI) imaging. Resonance-enhanced multiphoton ionization (REMPI), via two-photon excitation to the double-well EF 1Σ state, was used to state-selectively ionize the H2 and determine angular momentum distributions for H2 (ν = 0) and H2 (ν = 1). Velocity-map ion images were obtained for H2 (ν = 0 and 1, J = 5), allowing the total translational energy release of the photodissociation process to be determined. Following photolysis of CH3CHO in a gas cell, the CH2CO co-fragment was identified, using Fourier transform infrared spectroscopy, by its characteristic infrared absorption at 2150 cm-1. The measured quantum yield of the CH2CO + H2 product channel at 305.0 nm is φ = 0.0075 ± 0.0025 for both 15 Torr of neat CH3CHO and a mixture with 745 Torr of N2. Although small, this result has implications for the atmospheric photochemistry of carbonyls and this reaction represents a new tropospheric source of H2. Quasi-classical trajectory (QCT) simulations on a zero-point energy corrected reaction-path potential are also performed. The experimental REMPI and VMI image distributions are not consistent with the QCT simulations, indicating a non reaction-path mechanism should be considered.

Synthesis and characterization of silicon nanorod on n-type porous silicon.

This work reports a new method for growing semiconductor nanorods on a porous silicon substrate. After preparation of n-type porous silicon samples, a thin layer of gold was deposited on them. Gold deposited samples were annealed at different temperatures. The structural, thermal, and optical properties of the samples were studied using a field emission scanning electron microscope (FESEM), photoacoustic spectroscopy, and photoluminescence spectroscopy, respectively. FESEM analysis revealed that silicon nanorods of different sizes grew on the annealed samples. Thermal behavior of the samples was studied using photoacoustic spectroscopy. Photoluminescence spectroscopy showed that the emission peaks were degraded by gold deposition and attenuated for all samples by annealing.

Structural, optical, opto-thermal and thermal properties of ZnS-PVA nanofluids synthesized through a radiolytic approach.

This work describes a fast, clean and low-cost approach to synthesize ZnS-PVA nanofluids consisting of ZnS nanoparticles homogeneously distributed in a PVA solution. The ZnS nanoparticles were formed by the electrostatic force between zinc and sulfur ions induced by gamma irradiation at a dose range from 10 to 50 kGy. Several experimental characterizations were conducted to investigate the physical and chemical properties of the samples. Fourier transform infrared spectroscopy (FTIR) was used to determine the chemical structure and bonding conditions of the final products, transmission electron microscopy (TEM) for determining the shape morphology and average particle size, powder X-ray diffraction (XRD) for confirming the formation and crystalline structure of ZnS nanoparticles, UV-visible spectroscopy for measuring the electronic absorption characteristics, transient hot wire (THW) and photoacoustic measurements for measuring the thermal conductivity and thermal effusivity of the samples, from which, for the first time, the values of specific heat and thermal diffusivity of the samples were then calculated.