Isomerization kinetics of benzylic and methylphenyl type radicals in single-ring aromatics

Mutual isomerization through H-atom shifts in benzylic and methylphenyl type radicals are examined for toluene, and o-, m-, and p-xylene isomers. In the high temperature pyrolysis and oxidation of toluene, three possible methylphenyl radical isomers can be formed (2-, 3-, and 4-methylphenyl). The 2-methylphenyl radical may undergo a facile isomerization to benzyl through a four-membered ring critical structure – a pathway not accessible to 3- and 4-methylphenyl. Electronic structure calculations show that 2-methylphenyl isomerization to benzyl is preferred energetically by at least 20 kcal/mol over other possibilities. Monte Carlo RRKM/master equation simulations illustrate that, at temperatures ?1200 K, and for almost all pressures, the 2-methylphenyl radical has a lifetime of only several microseconds, whereas 3- and 4-methylphenyl radicals have a substantially longer lifetime, allowing them to react with other species, including molecular oxygen, during toluene oxidation. This is also found to be the case for all dimethylphenyl radicals in the three xylene isomers. As a result, the structure of the xylene isomers and specifically the number of H atoms immediately adjacent to the methyl groups can have a direct impact on their high-temperature oxidation and appear to explain the observed differences in xylene oxidation behind reflected shock waves and in laminar premixed flames.     

Master Equation Modeling of the Unimolecular Decompositions of α‐Hydroxyethyl (CH3CHOH) and Ethoxy (CH3CH2O) Radicals

The unimolecular decomposition of two radical isomers of C₂H₅O (CH₃CH₂O/ethoxy, CH₃CHOH/α‐hydroxyethyl) are investigated by means of Rice–Ramsperger–Kassel–Marcus/master equation simulations in helium and nitrogen bath gases on an accurate one‐dimensional potential energy surface. For ethoxy, simulations are carried out between temperatures of 406 and 1200 K and pressures of 0.001 and 100 atm. For CH₃CHOH, simulations are carried out between temperatures of 800 and 1500 K and pressures of 0.001 and 100 atm. Results are compared with available experimental data, with good agreement. The dominant product of α‐hydroxyethyl decomposition is CH₃CHO + H, with C₂H₃OH + H and CH₃ + CH₂O, being minor channels. Rate coefficients are strongly dependent on temperature and pressure and are recommended with attendant uncertainty factor estimates. The relative roles of vinyl alcohol and acetaldehyde in the context of combustion chemistry are also discussed.     

The Effect of Alcohol and Carbonyl Functional Groups on the Competition between Unimolecular Decomposition and Isomerization in C4 and C5 Alkoxy Radicals

Presented here are computed rates for the thermal unimolecular decomposition of a variety of alkoxy radicals with four‐ and five‐carbon length backbones. Three classes of molecules are examined: alkoxy radicals with saturated hydrocarbon backbones, those with alcohol functional groups, and those with carbonyl functional groups. The chosen species represent many of those found during the combustion of fossil fuels as well as bio‐derived alternatives. Density functional theory calculations were benchmarked against higher level coupled cluster calculations and used to explore the potential energy surfaces of these systems. Transition state theory was used to calculate high‐pressure limit rate coefficients of all radical intermediates in the regimes relevant to atmospheric chemistry and combustion. We show that the assumption that alkoxy radicals quickly decompose via β‐scission to aldehydes and other radicals is not valid for some of the alkoxy radicals investigated in this work. We further illustrate how intra‐H migrations in larger alkoxy radicals with carbonyl and alcohol functional groups can dominate unimolecular decomposition under combustion and atmospheric relevant conditions. Finally, we discuss why carbonyl groups can increase or decrease intra‐H migration barriers depending on their location relative to the transferring H‐atom.     

Dual Fluorescence and Photoprototropic Characteristics of 2-Aminodiphenylsulphone-β-Cyclodextrin Inclusion Complex

The absorption and fluorescence spectral characteristics of 2-aminodiphenylsulphone (2ADPS) have been investigated in the presence of β-cyclodextrin (β-CDx) in water. Dual emission is observed upon the complexation of 2ADPS in β-CDx. The stoichiometry of the host:guest inclusion complex is found to be 2:1. Steady state and time-resolved fluorescence spectral analysis support the formation of 2:1 complex between β-CDx and 2ADPS. The large enhancement in fluorescence intensity of twisted intramolecular charge transfer (TICT) band in aqueous β-CDx solution is due to the decrease in non-radiative processes. The ground and the excited state pK_a values for the monocation-neutral equilibrium of 2ADPS in β-CDx are found to be different from the pK_a values in aqueous solution. In the presence of β-CDx, 2ADPS is found to be less basic in the ground and the excited states.     

COMPARISON OF UV ACTION SPECTRA FOR LETHALITY AND MUTATION IN Salmonella typhimurium USING A BROAD BAND SOURCE AND MONOCHROMATIC RADIATIONS

Abstract— The UV-B region (280–320 nm) is thought to be primarily responsible for the mutagenic, lethal, and carcinogenic effects of solar radiation. We have conducted UV-B action spectroscopy for mutagenesis and survival of Ames' Salmonella typhimurium strain TA98 ( uvrB , pKM101) using both monochromatic radiation from a dye laser and broader bandwidth radiation emitted from FS-20 sunlamps. A series of optical filters having different transmission cut-offs together with the sunlamp source provided bandwidths having successively less short wavelength components from which a "broad band" action spectrum was deduced. The two sets of action spectra differed both qualitatively and quantitatively: in comparison to the monochromatic action spectra, the "broad band" spectra showed up to a 200-fold reduced efficiency for both mutation induction and lethality by UV-B wavelengths. These results suggest a large protective effect of the background UV-A and/or visible radiations which were present during the broad spectrum irradiations and which are also present in solar radiation. Additional experiments show that to the extent tested this protective effect is not due to photo-reactivation or irradiance (dose rate) effects     

Cloaking and imaging effects in plasmonic checkerboards of negative and and dielectric photonic crystal checkerboards

Negative refractive index materials are known to be able to support a host of surface plasmon states for both polarizations of light. This makes possible unique effects such as a perfect lens. Checkerboards consisting of alternating cells of positive and negative refractive index represent a very singular situation in which the density of modes diverges at the corners. This raises the question as to whether such effects will still be observed in a real dissipative system of finite size. We have considered several aspects of such structures including these and symmetry aspects (rectangular against triangular checkerboards). We have also studied silver checkerboards whose transverse extent is finite. Negative refractive index checkerboards bring new electromagnetic paradigms both through the intriguing possibilities they appear to offer, and the challenges they present to our understanding of the diffraction process. Most intriguing of all is the possibility of a triangular checkerboard lens whose resolution is limited not by wavelength, but only by the losses in the constituent materials, while a ray picture suggests it behaves as a perfect mirror. The resolution of this lens increases without limit as the losses tend to zero as shown by the generalized lens theorem. We finally show that light confinement can be achieved to certain extent using dielectric triangular photonic crystal (PC) checkerboards displaying the all-angle-negative-refraction (AANR) within the Bragg regime in p polarization. Effectively even a single rectangular or triangular PC can act as an open resonator that confines light in its neighborhood. This cloaking effect has been previously observed in PC slabs displaying the AANR effect. We show that the cloaking is enhanced for three triangular PC wedges sharing a vertex and further improved for 12 triangular PC wedges arranged in a checkerboard fashion.     

A metamaterial for directive emission

In this paper we present the first results on emission in metamaterial. We show how the specific properties of metallic composite material can modify the emission of an embedded source. We show that under proper conditions the energy radiated by a source embedded in a slab of metamaterial will be concentrated in a narrow cone in the surrounding media. An experimental demonstration of this effect is given in the microwave domain, and the constructed antenna has a directivity equivalent to the best reported results with photonic-crystal-based antennas but using a completely different physical principle [B. Temelkuaran, J. Appl. Phys. 87, 603 (2000)]].