Azobenzene is a prototypical photochromic molecule existing in two isomeric forms, which has numerous photochemical applications that rely on a precise knowledge of the molar absorption coefficients (ε). Careful analysis revealed that the previously reported absorption spectra of the "pure" isomers were in fact mutually contaminated by small amounts of the other isomer. Therefore, the absorption spectra of both trans- and cis-azobenzene in methanol were re-determined at temperatures of 5-45 °C. The thermodynamically more stable trans-azobenzene was prepared by warming the solution in the dark. To obtain the spectrum of cis-azobenzene three methods were used, which gave consistent results within the limits of error. The method based on the subtraction of derivative spectra coupled with a global analysis of the spectra recorded during thermal cis-trans isomerization is shown to give slightly more reliable results than the method using isomeric ratios determined by H-NMR. The described methods are readily generalizable to other azobenzene derivatives and to other photochromic systems. The practical implication of the re-determined ε values is demonstrated by a very high precision of spectrophotometric species analysis in azobenzene isomeric mixtures. The new ε values imply that the previously reported quantum yields must be revised.
The quantum yields of azobenzene photoisomerization in methanol solution were redetermined using newly obtained molar absorption coefficients of its cis- and trans-isomers. The results differ substantially from those published previously, especially in the range of the nπ* absorption band. Besides actinometry, these findings are relevant for applications of azobenzene derivatives in optical switching.
The concentration of hydroxyl (OH) radicals in a plasma pencil, an atmospheric RF plasma jet ignited in argon, was measured by laser-induced fluorescence calibrated by Rayleigh scattering on ambient air. A suitable excitation scheme for this discharge was suggested based on laser excitation to the lowest vibrational level of the A 2 + state. Effects of spectral overlap between the laser and absorption line, fluorescence saturation, temporal evolution of fluorescence radiation, rotational energy transfer and rotational distribution on the diagnostic method were analysed. The maximum OH concentration was approximately 5 × 10 20 m −3 . The maximum was reached when the measurement point localized in the effluent of the plasma pencil was inside but close to the tip of the visible active discharge.
A spatially resolved two-dimensional quantitative measurement of OH concentration in an effluent of a radio-frequency-driven atmospheric pressure plasma jet ignited in argon is presented. The measurement is supported by a gas dynamics model which gives detailed information about the spatially resolved gas composition and temperature. The volume in which the OH radicals were found and partially also the total amount of OH radicals increase with the argon flow rate, up to a value for which the flow becomes turbulent. In the turbulent regime, both the emission from the jet and the OH concentration are confined to a smaller volume. The maximum concentration of about 5.4 × 10 21 m −3 is reached at the tip of the visible discharge at the flow rate of 0.6 slm and high driving powers. An increase in hydroxyl concentration due to admixing of humid ambient air to the argon flow was observed.
The paper discusses the deposition of protective coatings ranging from organosilicon plasma polymers to SiO 2 -like films and hard diamond-like carbon/silicon oxide (DLC : SiO x ) coatings in radio frequency capacitively coupled discharges using hexamethyldisiloxane (HMDSO). As a result of the optimization of the deposition conditions it was possible to obtain high performance protective coatings. In the HMDSO/O 2 mixture, it was shown that rather than the SiO 2 -like film a hard cross-linked SiO x C y H z polymer film can be used as a protective coating for polycarbonate. The optimum conditions for the deposition of an almost stress-free film were 17% of HMDSO and dc bias voltage of −240 V. The film hardness and elastic modulus were 10 GPa and 75 GPa, respectively. The refractive index at 600 nm was 1.5 and the extinction coefficient decreased from 0.02 at 240 nm down to zero at 600 nm. The films deposited from HMDSO/CH 4 and HMDSO/CH 4 /H 2 mixtures exhibited the attractive properties of DLC films with the partial elimination of some of their drawbacks, such as absorption in the visible and a high intrinsic stress. The optimum concentration of the HMDSO was approximately 21%. Under these conditions the concentration of SiO x in the films was approximately 9 at.%. The film hardness and elastic modulus were above 22 GPa and 120 GPa, respectively.
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