A simple experimental method for determining optical second-order polarizabilities of organic molecules for second harmonic generation (SHG) is developed by using a two-level quantum mechanical model. Required values of excited-state dipole moments are obtained from a solvatochromic method based on the theoretical treatment of McRae. Second-order polarizabilities obtained by this method for a series of compounds compare well with those obtained by the conventional EFISH technique. The solvatochromic method has the important advantage that measurements can be made rapidly with simple equipment available in most chemistry laboratories.
Thin films for optical second-harmonic generation (SHG) were prepared from a newly designed and synthesized amorphous polymer that incorporated a high density of active nonlinear optical groups (p-nitroaniline as attached side groups). For alignment of the nonlinear groups a very high electric field was applied by a corona discharge to the polymer films above Tg (125 °C). The subsequent freezing process resulted in a polymer film initially exhibiting a very high second-order nonlinear coefficient, d33=31 pm/V, measured by the Maker-fringe technique, plus excellent thermal, mechanical, and optical properties. The dynamics of polar alignment and decay, studied by in situ poling (or depoling) and SHG measurements, indicated a multiple exponential behavior with the average relaxation time somewhat longer than expected from extrapolation of the dielectric relaxations data according to the Williams–Landel–Ferry equation. The frozen-in SHG behavior at room temperature (∼100 °C below Tg) relaxed after 5 days to a stabilized value of 19 pm/V for d33.
A multipass cell (MPC) design for laser absorption spectroscopy is presented. The development of this new type of optical cell was driven by stringent criteria for compactness, robustness, low volume, and ease of use in optical systems. A single piece of reflective toroidal surface forms a near-concentric cavity with a volume of merely 40 cm(3). Contrary to traditional MPCs, this design allows for flexible path-length adjustments by simply changing the aiming angle of the laser beam at the entrance window. Two effective optical path lengths of 2.2 and 4.1 m were chosen to demonstrate the cell's suitability for high-precision isotope ratio measurements of CO(2) at 1% and ambient mixing ratio levels.
In this paper we present two compact, quantum cascade laser absorption spectroscopy based, sensors developed for trace substance detection in gases and liquids. The gas sensor, in its most integrated version, represents the first system combining a quantum cascade laser and a quantum cascade detector. Furthermore, it uses a toroidal mirror cell with a volume of only 40 cm(3) for a path length of up to 4 m. The analytical performance is assessed by the measurements of isotope ratios of CO2 at ambient abundance. For the (13)CO2/(12)CO2 isotope ratio, a measurement precision of 0.2‰ is demonstrated after an integration time of 600 s. For the liquid sensor, a microfluidic system is used to extract cocaine from saliva into a solvent (PCE) transparent in the mid-infrared. This system is bonded on top of a Si/Ge waveguide and the concentration of cocaine in PCE is measured through the interaction of the evanescent part of the waveguide optical mode and the solvent flowing on top. A detection limit of <100 μg mL(-1) was achieved with this system and down to 10 μg mL(-1) with a simplified, but improved system.
Optical third-harmonic generation was used to measure third-order nonlinear susceptibilities χ(3) for thin films of planar zigzag polysilanes and polygermanes. A χ(3) of 11.3×10−12 esu was measured, the largest value ever reported for a polymer with transparency throughout the visible. The value of χ(3) was found to vary substantially with thermally induced reversible changes in polymer backbone conformation and also with film thickness.
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