Effective path length in attenuated total reflection spectroscopy

Attenuated total reflection (ATR) spectroscopy is now the most popular sampling technique for the measurement of infrared spectra of condensed phase samples. Most practitioners of ATR spectroscopy use the equation for depth of penetration, d(p), to estimate the path length of the evanescent wave through the sample. However, the effective path length, d(e), of the evanescent wave in an ATR measurement, i.e., the equivalent path length in a transmission measurement that would lead to an absorption band of the same intensity, is a more accurate metric than d(p). In measurements designed to obtain the absorptivity of bands in the spectrum of a strongly absorbing viscous liquid, we have shown that the refractive index used in the expressions for d(e) must be modified to take into account the effect of anomalous dispersion before accurate effective path lengths and band absorptivities can be measured.     

High-luminosity multipass cell for infrared imaging spectroscopy

An original imaging multipass cell for infrared spectroscopy has been designed and built. The cell design is aimed at overcoming intrinsic sensitivity limitations associated with the low specific spectral radiance power of blackbody sources. Owing to the implemented low f number, the detector collects a large amount of the energy emitted over a wide angle by a blackbody source. In addition, the adopted optical configuration allows maintenance of the same spatial distribution of the radiance pattern at the cell entrance and exit (imaging capability) within an aperture area of several square millimeters. This feature allows the use of uncollimated blackbody-type emitter arrays and infrared sensor arrays coupled with linear, spectrally variable filters, and performance of spectroscopic measurements of infrared absorption for low concentrated gases detection. In the present design the cell has an f number of about 2, and the optical path is ten times larger than the cell length.     

Comparison of methods for transfer of calibration models in near-infared spectroscopy: a case study based on correcting path length differences using fiber-optic transmittance probes in in-line near-infrared spectroscopy

This article addresses problems related to transfer of calibration models due to variations in distance between the transmittance fiber-optic probes. The data have been generated using a mixture design and measured at five different probe distances. A number of techniques reported in the literature have been compared. These include multiplicative scatter correction (MSC), path length correction (PLC), finite impulse response (FIR), orthogonal signal correction (OSC), piecewise direct standardization (PDS), and robust calibration. The quality of the predictions was expressed in terms of root mean square error of prediction (RMSEP). Robust calibration gave good calibration transfer results, while the other methods did not give acceptable results.     

Understanding colour reproduction in multispectral imaging: measuring camera sensor response in the ultraviolet,visible and infrared

The representation of colour in digital images is based on the response of camera used to capture the image, and how light interacts with the sensor in the respective red, green and blue channels. In Ultraviolet and Infrared, we have no reference for how they should look as we cannot directly observe them. A novel approach for the analysis of how a commercial SLR camera captures colour as a function of wavelength in the UV, visible and IR regions is presented here, along with a discussion on how the optical properties of filtration and sensor construction, impact the images produced.     

Variable pressure infrared diode laser spectroscopy: a new method for trace-gas monitoring

A new method for measuring trace concentrations of atmospheric pollutants by infrared diode laser spectroscopy has been devised. This method relies on the increase of the signal as the pressure inside the cell increases, while the frequency of the diode is stabilized on the line, even if it is unresolved. Performances of this method were tested with N2O and with 1,3-butadiene. As an example of application, we measured the butadiene emitted by car exhausts. Sensitivity and rapidity of this method are equivalent to the usual scanning method in which the whole line is described, but this new method benefits from its simplicity and robustness.     

Temperature effects on the optical path length of infrared liquid transmission cells

Infrared (IR) spectroscopy is widely used for studies of temperature-dependent properties of liquids and solutions, such as thermal denaturation of proteins and other molecules of biological interest. The variation of the spectroscopic signals with temperature can be affected by the changes in the optical path length due to the thermal expansion of the components of the sample cell. In this report we investigate the temperature dependence of the optical path length for a liquid IR sample cell of a design typical for aqueous solution experiments. The path lengths were measured from the interference fringes, both in dry cells and with cells partially filled with water. We found that the optical path length variations are significant, on the order of several percent within the temperature range used (0-87 °C). Several commercially available spacers (Teflon, mylar, and lead) and gaskets (Teflon, lead, silicone rubber, Viton, and neoprene) were tested to find materials with either the smallest or most reproducible effect. Teflon, due to its phase transition (known as the "knee point") near room temperature, leads to abrupt changes in path length when used as either spacer or gasket component. On the other hand, Teflon is preferred for its inertness, while several of the other tested materials, most notably lead, are not practically usable due to adhesion to the cell windows upon heating and contact with the aqueous sample. The combination that yielded the most reproducible results, with minimal complications due to adhesion, was Teflon spacer with neoprene gaskets. The implications of the optical path length changes for the temperature-dependent IR experiments and their possible corrections are discussed.     

An apparatus for infrared transmittance and reflectance measurements at cryogenic temperatures

A facility for measuring the optical properties of solid materials at cryogenic temperatures is being developed at the National Institute of Standards and Technology. A cryostat that houses four ur bolometric detectors and a six-position sample holder was designed and built. The bolometers operate near 5 K, and the sample temperature can he varied from 6 to 100 K. The beam from a Fourier transform spectrometer is directed to the cryostat by reflective optical components. The measurable wavelengths extend from 1m to 1 mm, with appropriate sources and beamsplitters in the spectrometer as well as windows and detectors in the cryostat. The angle of incidence on the sample ranges from 7.5 to 60. The mechanical electrical, and optical designs are described in this paper. Initial measurement results at wavelengths from 2 to 30m and a sample temperature of 10 K are presented.     

Multichannel moderate-bandwidth filter instrument for measurement of the ozone-column amount,cloud transmittance,and ultraviolet dose rates

A six-channel moderate-bandwidth filter instrument for measurement of UV and visible radiation has been developed. The characteristic of the instrument are described, including the spectral and the angular responses. Furthermore the calibration procedure is outlined. Combining information from several channels, one may determine the total ozone-column amount, various biological dose rates, a cloud transmission factor, and the effective cloud optical depth. The methods used to determine these parameters are presented, and the measured parameters are compared with similar ones obtained from other instruments. The total ozone as measured by the instrument agrees with measurements from a standard Brewer to -0.05% +/- 2.04% over a two-year period. Two weeks of cloudless Commission Internationale de L'Eclairage dose rates agree with those from a Bentham double monochromator spectroradiometer to 0.99 +/- 0.03.     

Broad-band superachromatic retarders and circular polarizers for the UV,visible and near infrared

Abstract

We present designs for two combinations of conventional achromatic retarders that can be used, over the wavelength range from 300 to 1100 nm, to obtain retardations of a quarter-wave and a half-wave, respectively, as well as a combination that can be used as a circular polarizer over this range of wavelengths.     

Superconducting single-photon detector for the visible and infrared spectral range

Abstract

We present results on dark count rates and spectral sensitivities of superconducting single-photon detectors in the visible and near-infrared spectral range. The active detector element is a nanometre-sized (a few nanometres thick and less than 100nm wide) meander line carrying a supercurrent. The superconducting materials are NbN and Nb, respectively. The NbN detector exhibited a flat spectral sensitivity up to about 2.4μm. Fluctuations of the superconducting order parameter are considered as a major source of dark count events. A simple model and its limitations to explain the observed dark count rates is discussed.     

Gas-phase databases for quantitative infrared spectroscopy

The National Institute of Standards and Technology (NIST) and the Pacific Northwest National Laboratory (PNNL) are each creating quantitative databases containing the vapor-phase infrared spectra of pure chemicals. The digital databases have been created with both laboratory and remote-sensing applications in mind. A spectral resolution of approximate, equals 0.1 cm(-1) was selected to avoid degrading sharp spectral features, while also realizing that atmospheric broadening typically limits line widths to 0.1 cm(-1). Calculated positional (wave- number, cm(-1)) uncertainty is /=9) path length-concentration burdens and fitting a weighted Beer's law plot to each wavenumber channel. The two databases include different classes of compounds and were compared using 12 samples. Though these 12 samples span a range of polarities, absorption strengths, and vapor pressures, the data agree to within experimental uncertainties with only one exception.     

Laboratory studies of alkali metal filter deposition, ultraviolet transmission, and visible blocking

Far-ultraviolet alkali metal or Wood's filters have been produced and tested supporting the production of a flight filter for the Wide Field Planetary Camera 2 on the Hubble Space Telescope. Sodium layers 0.5-1-mum thick transmit up to 40% in the ultraviolet while efficiently blocking visible wavelengths. The prevention of visible pinholes is assisted by a clean, sleek-free surface and a cooled substrate during deposition. The coatings are stabilized efficiently by a bismuth overcoating whose transmission spectrum is presented. We also report for the first time, to our knowledge, the first demonstrated long-wavelength cutoff from a lithium filter, with a shorter cutoff wavelength than sodium and potentially higher stability for astronomical imaging.     

A modular path length corrector for recirculating linacs

We present a novel modular magnetic system that can introduce a large and continuously variable path length difference without simultaneous variation of the longitudinal dispersion. This is achieved by using a combination of an electrically adjustable magnetic chicane and a mechanically adjustable focusing chicane. We describe how such a system may be made either isochronous or with a given longitudinal dispersion, and show that the nonlinear terms in such a system are relatively small.     

Controlling the optical path length in turbid media using differential path-length spectroscopy: fiber diameter dependence

We have characterized the path length for the differential path-length spectroscopy (DPS) fiber optic geometry for a wide range of optical properties and for fiber diameters ranging from 200 microm to 1000 microm. Phantom measurements show that the path length is nearly constant for scattering coefficients in the range 5 mm(-1)< micros <50 mm(-1) for all fiber diameters and that the path length is proportional to the fiber diameter. The path length decreases with increasing absorption for all fiber diameters, and this effect is more pronounced for larger fiber diameters. An empirical model is formulated that relates the DPS path length to total absorption for all fiber diameters simultaneously.     

Hyperspectral imager, from ultraviolet to visible, with a KDP acousto-optic tunable filter

Hyperspectral imaging in the ultraviolet to visible spectral region has applications in astronomy, biology, chemistry, medical sciences, etc. A novel electronically tunable, random-wavelength access, compact, no-moving-parts, vibration-insensitive, computer-controlled hyperspectral imager operating from 220 to 480 nm with a spectral resolution of 160 cm(-1), e.g., 2 nm at 350 nm, has been developed by use of a KDP acousto-optic tunable filter (AOTF) with an enhanced CCD camera and a pair of crossed calcite Glan-Taylor polarizing prisms. The linear and angular apertures of the AOTF are 1.5 x 1.5 cm2 and 1.2 degrees, respectively. Imager setup and spectral imaging results as well as analyses and discussion of various factors affecting image quality are presented.