Multiple-pass or long path absorption cells are commonly used in
spectroscopy
Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter wa ...
to measure low-concentration components or to observe weak spectra in gases or liquids. Several important advances were made in this area beginning in the 1930s, and research into a wide range of applications continues to the present day.
Functional Overview
Generally the goal of this type of sample cell is to improve detection sensitivity by increasing the total optical path length that travels through a small, constant sample volume. In principle, a longer
path length results in greater detection sensitivity. Focusing mirrors must be used to redirect the beam at each reflection point, resulting in the beam being restricted to a predefined space along a controlled path until it exits the
optical cavity An optical cavity, resonating cavity or optical resonator is an arrangement of mirrors or other optical elements that forms a cavity resonator for light waves. Optical cavities are a major component of lasers, surrounding the gain medium and provi ...
. The output of the cell is the input of an optical detector (a specialized type of
transducer
A transducer is a device that converts energy from one form to another. Usually a transducer converts a signal in one form of energy to a signal in another.
Transducers are often employed at the boundaries of automation, measurement, and contr ...
), which senses specific changes in the properties of the beam that occur during interaction with the
test sample. For instance, the sample may absorb
energy
In physics, energy (from Ancient Greek: ἐνέργεια, ''enérgeia'', “activity”) is the quantitative property that is transferred to a body or to a physical system, recognizable in the performance of work and in the form of heat a ...
from the beam, resulting in an
attenuation
In physics, attenuation (in some contexts, extinction) is the gradual loss of flux intensity through a medium. For instance, dark glasses attenuate sunlight, lead attenuates X-rays, and water and air attenuate both light and sound at variable att ...
of the output that is detectable by the transducer. Two conventional multipass cells are called the White cell and Herriott cell.
Pfund Cell
In the late 1930s
August Pfund used a triple-pass cell like the one shown above for atmospheric study. The cell, which became known as the Pfund cell, is constructed using two identical spherical mirrors, each having a hole carefully machined into its center. The separation distance between the mirrors is equal to the mirror focal length. A source enters from a hole in either mirror, is redirected twice at two reflection points, and then exits the cell through the other mirror on the third pass. The Pfund cell was one of the earliest examples of this type of spectroscopic technique and is noted for having used multiple passes.
White cell
The White cell was first described in 1942 by
John U. White in his paper ''Long Optical Paths of Large Aperture'',
and was a significant improvement over previous long path
spectroscopic measurement techniques. A White cell is constructed using three spherical,
concave mirror
A curved mirror is a mirror with a curved reflecting surface. The surface may be either ''convex'' (bulging outward) or ''concave'' (recessed inward). Most curved mirrors have surfaces that are shaped like part of a sphere, but other shapes are ...
s having the same radius of curvature. The mirrors are separated by a distance equal to their radii of curvature. The animation on the right shows a White Cell in which a beam makes eight
reflective
Reflection is the change in direction of a wavefront at an interface between two different media so that the wavefront returns into the medium from which it originated. Common examples include the reflection of light, sound and water waves. The ' ...
passes or traversals. The number of traversals can be changed quite easily by making slight rotational adjustments to either M2 or M3; however, the total number of traversals must always occur in multiples of four. The entering and exiting beams do not change position as traversals are added or removed, while the total number of traversals can be increased many times without changing the volume of the cell, and therefore the total optical path length can be made large compared to the volume of the sample under test. The spots from various passes can overlap on mirrors M2 and M3 but must be distinct on mirror M1. If the input beam is focused in the plane of M1, then each round trip will also be focused in this plane. The tighter the focus, the more nonoverlapping spots there can be on M1 and thus the higher the maximum pathlength.
At present the White cell is still the most commonly used multipass cell and provides many advantages.
For example,
* The number of traversals is easily controlled
* It allows for high numerical aperture
* It is reasonably stable (but not as stable as the Herriott cell)
White cells are available with path lengths ranging from less than a meter to many hundreds of meters.
[
]
Herriott cell
The Herriott cell first appeared in 1965 when
Donald R. Herriott
Donald R. Herriott (February 4, 1928 – November 8, 2007) was an American physicist who is known for his contributions to interferometry, and for his efforts towards perfecting the techniques of high-resolution lithography. Herriott also helped b ...
and Harry J. Schulte published ''Folded Optical Delay Lines'' while at
Bell Laboratories
Nokia Bell Labs, originally named Bell Telephone Laboratories (1925–1984),
then AT&T Bell Laboratories (1984–1996)
and Bell Labs Innovations (1996–2007),
is an American industrial research and scientific development company owned by mult ...
.
The Herriott cell is made up of two opposing spherical mirrors. A hole is machined into one of the mirrors to allow the input and output beams to enter and exit the cavity. Alternatively, the beam may exit through a hole in the opposite mirror. In this fashion the Herriott cell can support multiple light sources by providing multiple entrance and exit holes in either of the mirrors. Unlike the White cell, the number of traversals is controlled by adjusting the separation distance D between the two mirrors. This cell is also commonly used and has some advantages
[ over the White cell:
* It is simpler than the White cell with only two mirrors that are easier to position and less susceptible to mechanical disturbance of the cell
* Can be more stable than the White cell
However, the Herriot cell does not accept high numerical aperture beams. In addition, larger sized mirrors must be used when longer path lengths are needed.
]
Circular Multipass Cells
Another category of multipass cells is generally referred to as circular multipass reflection cells. They were first introduced by Thoma and co-workers in 1994. Such cells rely on a circular arrangement of mirrors. The beam enters the cell under an angle and propagates on a star-shaped pattern (see picture on the right). The path length in circular multipass cells can be varied by adjusting the incidence angle of the beam. An advantage lies in their robustness towards mechanical stress such as vibrations or temperature changes. Furthermore, circular multipass cells stand out because of the small detection volumes they provide. A stable beam propagation is achieved by shaping individual reflection points to form a non-concentric mirror-arrangement.
In a special case, a circular mirror is used, allowing continuous adjustment of the angle of incidence. A drawback of this circular cell configuration is the inherent concentric mirror arrangement which leads to imperfect imaging after a large number of reflections.
See also
* Laser absorption spectrometry
Laser absorption spectrometry (LAS) refers to techniques that use lasers to assess the concentration or amount of a species in gas phase by absorption spectrometry (AS).
Optical spectroscopic techniques in general, and laser-based techniques in ...
* Tunable diode laser absorption spectroscopy
* Optical system
* Absorption spectroscopy
* Infrared spectroscopy
Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or function ...
* Absorption (optics)
* Optical density
Absorbance is defined as "the logarithm of the ratio of incident to transmitted radiant power through a sample (excluding the effects on cell walls)". Alternatively, for samples which scatter light, absorbance may be defined as "the negative lo ...
* Optical depth
In physics, optical depth or optical thickness is the natural logarithm of the ratio of incident to ''transmitted'' radiant power through a material.
Thus, the larger the optical depth, the smaller the amount of transmitted radiant power through ...
* Reflectivity
The reflectance of the surface of a material is its effectiveness in reflecting radiant energy. It is the fraction of incident electromagnetic power that is reflected at the boundary. Reflectance is a component of the response of the electronic ...
References
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Optical devices
Physical chemistry
Spectroscopy