We have developed a technique which allows optical absorption measurements to be made using a pulsed light source and offers a sensitivity significantly greater than that attained using stabilized continuous light sources. The technique is based upon the measurement of the rate of absorption rather than the magnitude of absorption of a light pulse confined within a closed optical cavity. The decay of the light intensity within the cavity is a simple exponential with loss components due to mirror loss, broadband scatter (Rayleigh, Mie), and molecular absorption. Narrowband absorption spectra are recorded by scanning the output of a pulsed laser (which is injected into the optical cavity) through an absorption resonance. We have demonstrated the sensitivity of this technique by measuring several bands in the very weak forbidden b1Σg−X3Σg transition in gaseous molecular oxygen. Absorption signals of less than 1 part in 106 can be detected.

Cavity ring‐down optical spectrometer for absorption measurements using pulsed laser sources

The detection and measurement of gas concentrations using the characteristic optical absorption of the gas species is important for both understanding and monitoring a variety of phenomena from industrial processes to environmental change. This study reviews the field, covering several individual gas detection techniques including non-dispersive infrared, spectrophotometry, tunable diode laser spectroscopy and photoacoustic spectroscopy. We present the basis for each technique, recent developments in methods and performance limitations. The technology available to support this field, in terms of key components such as light sources and gas cells, has advanced rapidly in recent years and we discuss these new developments. Finally, we present a performance comparison of different techniques, taking data reported over the preceding decade, and draw conclusions from this benchmarking.

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Optical gas sensing: a review

Dual-comb spectroscopy is an emerging new spectroscopic tool that exploits the frequency resolution, frequency accuracy, broad bandwidth, and brightness of frequency combs for ultrahigh-resolution, high-sensitivity broadband spectroscopy. By using two coherent frequency combs, dual-comb spectroscopy allows a sample’s spectral response to be measured on a comb tooth-by-tooth basis rapidly and without the size constraints or instrument response limitations of conventional spectrometers. This review describes dual-comb spectroscopy and summarizes the current state of the art. As frequency comb technology progresses, dual-comb spectroscopy will continue to mature and could surpass conventional broadband spectroscopy for a wide range of laboratory and field applications.

Dual-comb spectroscopy

Using the scanning imaging absorption spectrometer for atmospheric chartography (SCIAMACHY) pre-flight model satellite spectrometer, gas-phase absorption spectra of the most important atmospheric trace gases (O3, NO2, SO2, O2, OClO, H2CO, H2O, CO, CO2, CH4, and N2O) have been measured in the 230–2380 nm range at medium spectral resolution and at several temperatures between 203 and 293 K. The spectra show high signal-to-noise ratio (between 200 up to a few thousands), high baseline stability (better than 10−2) and an accurate wavelength calibration (better than 0.01 nm) and were scaled to absolute absorption cross-sections using previously published data. The results are important as reference data for atmospheric remote-sensing and physical chemistry. Amongst other results, the first measurements of the Wulf bands of O3 up to their origin above 1000 nm were made at five different temperatures between 203 and 293 K, the first UV-Vis absorption cross-sections of NO2 in gas-phase equilibrium at 203 K were recorded, and the ultraviolet absorption cross-sections of SO2 were measured at five different temperatures between 203 and 296 K. In addition, the molecular absorption spectra were used to improve the wavelength calibration of the SCIAMACHY spectrometer and to characterize the instrumental line shape (ILS) and straylight properties of the instrument. It is demonstrated that laboratory measurements of molecular trace gas absorption spectra prior to launch are important for satellite instrument characterization and to validate and improve the spectroscopic database.

Measurements of molecular absorption spectra with the SCIAMACHY pre-flight model: instrument characterization and reference data for atmospheric remote-sensing in the 230–2380 nm region

Diffuse reflectance measurements by infrared Fourier transform spectrometry

THE measurement of the vapor phase spectra T of compounds having high boiling points presents an experimental problem that may be solved either by heating the absorption cells or by making them very long. In the infra-red region radiation from the hot gases in heated cells decreases the accuracy of absorption measurements. If only a small amount of sample is available, the only possibility is to use an optical system in which the radiation goes back and forth through the same volume a large number of times. Several designs for such systems have been published recently1' 2 but none of them permits the use of large angular apertures at points off the optic axis. In this paper an absorption cell is described in which the light traverses a small volume a large and arbitrarily variable number of times, and in which the angular aperture of the mirrors is not occulted either on or off the optical axis. The design gives very high light transmission and can be used for observing spectra that are very weak, or that belong to high boiling point compounds or to compounds obtainable only in very low concentrations. It can be used for any liquids or gases that do not injure the mirror surfaces, with which they are directly in contact. The essential parts of the equipment are three spherical, concave mirrors that all have the same radius of curvature. These are set up as shown in Fig. 1 with two mirrors A and A' close together at one end of the absorption cell, and the third mirror B at the other end. The centers of curvature of A and A' are on the front surface of B, and the center of curvature of B is halfway between A and A'. This arrangement establishes a system of conjugate foci on the reflecting surfaces of the mirrors, by which all the light leaving any point on A is brought to a focus by B at the corresponding point on A', and all the light leaving this point on A' is focused back again to the

Long Optical Paths of Large Aperture

Two different multiple traversal optical systems are described; one gives the longest paths, the other the best compensation for vibration and misalignment problems. In the first, seven mirrors in a near confocal arrangement permit a large aperture beam of light to pass through a restricted volume for a discrete and very large number of times. A rectangular array of images corresponding to different numbers of passes appears on four mirrors at one end of the system. At the other end, three mirrors form the array and illuminate each image in it from one or more different directions. The possible numbers of passes are (4mn − 2)k + 2, where m and n are any integers representing, respectively, the number of columns and half the number of rows in the array. k is the number of different directions from which the array is illuminated. Geometrically, the beam may be isolated after thousands of passes; practically, the number is limited by reflection losses. In the second system the addition of four diagonal mirrors to a White cell converts the two lines of images on the single mirror to a rectangular array of images, almost squaring the maximum possible number of passes. With multiples of four rows of images in the array, the position of the output image is invariant to small errors in alignment of the mirrors.

Very long optical paths in air

A photoelectric Raman spectrometer has been built for the measurement of small liquid and gas samples. Employing a 1200-line per millimeter replica grating, it can record a complete Raman spectrum in six minutes and a more accurate one in an hour. The precision of repeat readings is ±1 percent. Five-milliliter liquid samples are normally used, and methods are described for reducing the size to less than one milliliter.

Photoelectric Raman spectrometer

A long path gas absorption cell especially suited for infrared analyses of components of extremely low concentrations and absorption coefficients is described. The cell can be evacuated or pressurized. With aluminized mirrors and KBr field lenses, the evacuated cell performs with a peak efficiency of 45 percent of incident energy at 10 meters path length. Path length is adjustable by 1.25-meter increments from 1.25 meters to 10 meters. Adjustments are simple and can be made in a matter of a few minutes with good reproducibility. The cell will attach to the Perkin-Elmer Models 12, 112, and 21 spectrometers with compatibility to other attachments. The optical path can be altered quickly so that the usual sampling space of the spectrometer is available.

A Long Path Gas Absorption Cell

In a new method of measuring diffuse reflectance in the infrared, the sample is irradiated from all directions with chopped light The source and sample are placed at conjugate foci of a hemispherical mirror with the chopper between the source and mirror, making the component reflected by the sample distinguishable from the one emitted by it Advantages are that reflectance may be measured over a very wide range of sample temperatures and that heating of the sample is relatively small By adding another chopper after the sample, the emitted component may be recorded as an indication of sample temperature under the conditions of measurement When calibrated against an aluminum mirror, the reflectance of a thin layer of MgO smoke on a mirror is measured as 99% at 25 μ The performance of the system is illustrated with a number of spectra

John U. White

Papers

Long Optical Paths of Large Aperture

Very long optical paths in air

Photoelectric Raman spectrometer

A Long Path Gas Absorption Cell

New Method for Measuring Diffuse Reflectance in the Infrared