Abstract

The design of and initial results obtained from a multipass matrix system (MMS) for mid-infrared spectroscopy that operates in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) recently constructed in the School of Chemistry at the University of Leeds, is described. HIRAC is an evacuable, temperature variable, photochemical atmospheric reaction chamber. The MMS design is a modified Chernin cell, utilizing three objective mirrors and two field mirrors. In addition to providing the paraxial equations required for design of a throughput matched multipass cell and throughput matched transfer optics, advanced ray tracing simulations have been performed for the Chernin design described herein. The simulations indicate that, for this MMS, which features small off-axis angles and preserves perfectly the focal properties of the original White design, the paraxial equations are nearly exact, throughput losses due to astigmatism are insignificant, and the system has zero theoretical geometric loss. Measurements of the signal incident on the detector at different matrix arrangements confirm the ray trace results, suggesting that geometric loss in this system is insignificant. The MMS described herein provides adequate stability to permit measurements while the chamber mixing fans are on, gives very good detection limits for some representative species, and is easy to align.

© 2007 Optical Society of America

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References

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  1. H. W. Biermann, E. C. Tuazon, A. M. Winer, T. J. Wallington, and J. N. Pitts, "Simultaneous absolute measurements of gaseous nitrogen species in urban ambient air by long path length infrared and ultraviolet-visible spectroscopy," Atmos. Environ. 22, 1545-1554 (1988).
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef] [PubMed]
  12. P. Hannan, "White cell design considerations," Opt. Eng. 28, 1180-1184 (1989).
  13. T. Ahonen, S. Alanko, V. M. Horneman, M. Koivusaari, R. Paso, A. M. Tolonen, and R. Anttila, "A long path cell for the Fourier spectrometer Bruker IFS 120 HR: application to the weak nu(1)+nu(2) and 3 nu(2) bands of carbon disulfide," J. Mol. Spectrosc. 181, 279-286 (1997).
    [CrossRef]
  14. N. Oldham, Oldham Optical, Scarborough, UK (personal communication, 2006).
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    [CrossRef] [PubMed]
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    [CrossRef] [PubMed]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [PubMed]
  26. S. Chernin and E. Barskaya, "Optical multipass matrix systems," Appl. Opt. 30, 51-58 (1991).
    [CrossRef] [PubMed]
  27. S. M. Chernin, "New generation of multipass systems in high resolution spectroscopy," Spectrochim. Acta Part A 52, 1009-1022 (1996).
    [CrossRef]
  28. D. R. Glowacki, A. Goddard, K. Hemavibool, F. Anderson, W. J. Bloss, R. Commane, D. E. Heard, T. Ingham, T. Malkin, M. J. Pilling, and P. W. Seakins, "Design and initial results of a highly instrumented photochemical reactor for characterisation of atmospheric chemical processes (HIRAC)," Atmos. Chem. Phys. Discuss. 7, 10687-10742 (2007).
    [CrossRef]
  29. P. R. Griffiths and J. A. Haseth, Fourier Transform Infrared Spectrometry (Wiley, 1986).
  30. W. B. Olson, "Method for first-order design of a transfer optics system to throughput match a Fourier transform spectrometer to a sample cell without use of a field lens at the cell input," Appl. Opt. 26, 2441-2445 (1987).
    [CrossRef] [PubMed]
  31. "OptisWorks," http://www.optis-world.com/OPTISWORKS/optisworks_cooperative.htm?soft_id=3 at the time of submission.
  32. A. Cornejo-Rodriguez, "Ronchi Test," in Optical Shop Testing, D. Malacara, ed. (Wiley, 2007).
  33. I. Barnes, K. H. Becker, and N. Mihalopoulos, "An FTIR product study of the photooxidation of dimethyl disulfide," J. Atmos. Chem. 18, 267-289 (1994).
    [CrossRef]
  34. I. Barnes, University of Wuppertal, Wuppertal, Germany (personal communication, 17 November 2004).

2007 (1)

D. R. Glowacki, A. Goddard, K. Hemavibool, F. Anderson, W. J. Bloss, R. Commane, D. E. Heard, T. Ingham, T. Malkin, M. J. Pilling, and P. W. Seakins, "Design and initial results of a highly instrumented photochemical reactor for characterisation of atmospheric chemical processes (HIRAC)," Atmos. Chem. Phys. Discuss. 7, 10687-10742 (2007).
[CrossRef]

2006 (1)

D. E. Heard, "Atmospheric field measurements of the hydroxyl radical using laser-induced fluorescence spectroscopy," Ann. Rev. Phys. Chem. 57, 191-216 (2006).
[CrossRef]

2002 (1)

2001 (3)

S. M. Chernin, "Development of optical multipass matrix systems," J. Mod. Opt. 48, 619-632 (2001).

D. W. Steyert, J. M. Sirota, and M. E. Mickelson, "Two new long-pass cells for infrared and visible spectroscopy," Rev. Sci. Instrum. 72, 4337-4343 (2001).
[CrossRef]

L. Grassi and R. Guzzi, "Theoretical and practical consideration of the construction of a zero-geometric-loss multiple-pass cell based on the use of monolithic mutliple-face retroreflectors," Appl. Opt. 40, 6062-6071 (2001).
[CrossRef]

1999 (1)

1997 (1)

T. Ahonen, S. Alanko, V. M. Horneman, M. Koivusaari, R. Paso, A. M. Tolonen, and R. Anttila, "A long path cell for the Fourier spectrometer Bruker IFS 120 HR: application to the weak nu(1)+nu(2) and 3 nu(2) bands of carbon disulfide," J. Mol. Spectrosc. 181, 279-286 (1997).
[CrossRef]

1996 (2)

1994 (1)

I. Barnes, K. H. Becker, and N. Mihalopoulos, "An FTIR product study of the photooxidation of dimethyl disulfide," J. Atmos. Chem. 18, 267-289 (1994).
[CrossRef]

1992 (1)

1991 (1)

1989 (1)

P. Hannan, "White cell design considerations," Opt. Eng. 28, 1180-1184 (1989).

1988 (1)

H. W. Biermann, E. C. Tuazon, A. M. Winer, T. J. Wallington, and J. N. Pitts, "Simultaneous absolute measurements of gaseous nitrogen species in urban ambient air by long path length infrared and ultraviolet-visible spectroscopy," Atmos. Environ. 22, 1545-1554 (1988).
[CrossRef]

1987 (2)

R. E. Shetter, J. A. Davidson, C. A. Cantrell, and J. G. Calvert, "Temperature variable long path cell for absorption measurements," Rev. Sci. Instrum. 58, 1427-1428 (1987).
[CrossRef]

W. B. Olson, "Method for first-order design of a transfer optics system to throughput match a Fourier transform spectrometer to a sample cell without use of a field lens at the cell input," Appl. Opt. 26, 2441-2445 (1987).
[CrossRef] [PubMed]

1984 (1)

1976 (1)

1971 (2)

D. Horn and G. C. Pimentel, "2.5-km low temperature multiple reflection cell," Appl. Opt. 10, 1892-1898 (1971).
[CrossRef] [PubMed]

P. L. Hanst, "Spectroscopic methods for air pollution measurement," Adv. Environ. Sci. Technol. 2, 91-213 (1971).

1965 (1)

1961 (1)

1951 (1)

1948 (1)

H. J. Bernstein and J. Herzberg, "Rotation-vibration spectra of diatomic and simple polyatomic molecules with long absorbing paths," J. Chem. Phys. 16, 30-39 (1948).
[CrossRef]

1942 (1)

Adv. Environ. Sci. Technol. (1)

P. L. Hanst, "Spectroscopic methods for air pollution measurement," Adv. Environ. Sci. Technol. 2, 91-213 (1971).

Ann. Rev. Phys. Chem. (1)

D. E. Heard, "Atmospheric field measurements of the hydroxyl radical using laser-induced fluorescence spectroscopy," Ann. Rev. Phys. Chem. 57, 191-216 (2006).
[CrossRef]

Appl. Opt. (9)

L. Grassi and R. Guzzi, "Theoretical and practical consideration of the construction of a zero-geometric-loss multiple-pass cell based on the use of monolithic mutliple-face retroreflectors," Appl. Opt. 40, 6062-6071 (2001).
[CrossRef]

J. F. Doussin, R. Dominique, and C. Patrick, "Multiple-pass cell for very-long-path infrared spectroscopy," Appl. Opt. 38, 4145-4150 (1999).
[CrossRef]

D. C. Tobin, L. Strow, J. Lafferty, and W. B. Olson, "Experimental investigation of the self and N2 broadened continuum within the v2 band of water vapor," Appl. Opt. 35, 4724-4734 (1996).
[CrossRef] [PubMed]

D. Horn and G. C. Pimentel, "2.5-km low temperature multiple reflection cell," Appl. Opt. 10, 1892-1898 (1971).
[CrossRef] [PubMed]

W. B. Olson, "Minimization of volume and astigmatism in White cells for use with circular sources and apertures," Appl. Opt. 23, 1580-1585 (1984).
[CrossRef] [PubMed]

S. M. Chernin, S. B. Mikhailov, and E. G. Barskaya, "Aberrations of a multipass matrix system," Appl. Opt. 31, 765-769 (1992).
[CrossRef] [PubMed]

D. R. Herriott and H. J. Schulte, "Folded optical delay lines," Appl. Opt. 4, 883-889 (1965).
[CrossRef]

S. Chernin and E. Barskaya, "Optical multipass matrix systems," Appl. Opt. 30, 51-58 (1991).
[CrossRef] [PubMed]

W. B. Olson, "Method for first-order design of a transfer optics system to throughput match a Fourier transform spectrometer to a sample cell without use of a field lens at the cell input," Appl. Opt. 26, 2441-2445 (1987).
[CrossRef] [PubMed]

Atmos. Chem. Phys. Discuss. (1)

D. R. Glowacki, A. Goddard, K. Hemavibool, F. Anderson, W. J. Bloss, R. Commane, D. E. Heard, T. Ingham, T. Malkin, M. J. Pilling, and P. W. Seakins, "Design and initial results of a highly instrumented photochemical reactor for characterisation of atmospheric chemical processes (HIRAC)," Atmos. Chem. Phys. Discuss. 7, 10687-10742 (2007).
[CrossRef]

Atmos. Environ. (1)

H. W. Biermann, E. C. Tuazon, A. M. Winer, T. J. Wallington, and J. N. Pitts, "Simultaneous absolute measurements of gaseous nitrogen species in urban ambient air by long path length infrared and ultraviolet-visible spectroscopy," Atmos. Environ. 22, 1545-1554 (1988).
[CrossRef]

J. Atmos. Chem. (1)

I. Barnes, K. H. Becker, and N. Mihalopoulos, "An FTIR product study of the photooxidation of dimethyl disulfide," J. Atmos. Chem. 18, 267-289 (1994).
[CrossRef]

J. Chem. Phys. (1)

H. J. Bernstein and J. Herzberg, "Rotation-vibration spectra of diatomic and simple polyatomic molecules with long absorbing paths," J. Chem. Phys. 16, 30-39 (1948).
[CrossRef]

J. Mod. Opt. (1)

S. M. Chernin, "Development of optical multipass matrix systems," J. Mod. Opt. 48, 619-632 (2001).

J. Mol. Spectrosc. (1)

T. Ahonen, S. Alanko, V. M. Horneman, M. Koivusaari, R. Paso, A. M. Tolonen, and R. Anttila, "A long path cell for the Fourier spectrometer Bruker IFS 120 HR: application to the weak nu(1)+nu(2) and 3 nu(2) bands of carbon disulfide," J. Mol. Spectrosc. 181, 279-286 (1997).
[CrossRef]

J. Opt. Soc. Am. (4)

Opt. Eng. (1)

P. Hannan, "White cell design considerations," Opt. Eng. 28, 1180-1184 (1989).

Opt. Express (1)

Rev. Sci. Instrum. (2)

D. W. Steyert, J. M. Sirota, and M. E. Mickelson, "Two new long-pass cells for infrared and visible spectroscopy," Rev. Sci. Instrum. 72, 4337-4343 (2001).
[CrossRef]

R. E. Shetter, J. A. Davidson, C. A. Cantrell, and J. G. Calvert, "Temperature variable long path cell for absorption measurements," Rev. Sci. Instrum. 58, 1427-1428 (1987).
[CrossRef]

Spectrochim. Acta Part A (1)

S. M. Chernin, "New generation of multipass systems in high resolution spectroscopy," Spectrochim. Acta Part A 52, 1009-1022 (1996).
[CrossRef]

Other (8)

D. Ritz, M. Hausmann, and U. Platt, "An improved open path multi-reflection cell for the measurement of NO2 and NO3," in Optical Methods in Atmosperic Chemistry: Proceedings of the Meeting, Berlin, Germany, June 22-24, 1992, H. I. S. A. U. Platt, ed. (Proc. SPIE 1715, 1992), pp. 200-211.

I. Barnes, University of Wuppertal, Wuppertal, Germany (personal communication, 17 November 2004).

P. R. Griffiths and J. A. Haseth, Fourier Transform Infrared Spectrometry (Wiley, 1986).

"OptisWorks," http://www.optis-world.com/OPTISWORKS/optisworks_cooperative.htm?soft_id=3 at the time of submission.

A. Cornejo-Rodriguez, "Ronchi Test," in Optical Shop Testing, D. Malacara, ed. (Wiley, 2007).

K. H. Becker, "EUPHORE, The European Photoreactor," The construction and operation of an outdoor smog chamber in Valencia for studying mechanisms of photochemical processes and their modeling in the polluted air of different European regions. Design and technical development of the European photoreactor and first experimental results. Final Report, DG 12 contract EV5V-CT92-0059, (European Community, Brussels, 1996).

A. Fried and D. Richter, "Infrared absorption spectroscopy," in Analytical Techniques for Atmospheric Measurement, D.E.Heard, ed. (Blackwell, 2006), pp. 72-146.
[CrossRef]

N. Oldham, Oldham Optical, Scarborough, UK (personal communication, 2006).

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Figures (6)

Fig. 1
Fig. 1

Diagram of the field mirror shape, retroreflector orientation, input and output beam location, spot pattern, and location of the centers of curvature of the objective mirrors for the first six multipass arrangements featured in Table 1.

Fig. 2
Fig. 2

Arrangement of the modified three objective MMS showing the image locations on the field mirrors, F1 and F2, for a 72 pass system. The location of the centers of curvature of the objective mirrors, O1–O3, is also shown.

Fig. 3
Fig. 3

(a) Arrangement of the field images in the modified three objective MMS for a 48 pass system. The location of the centers of curvature of the objective mirrors, O1–O3, are also shown. The distance between the centers of each image in consecutive rows, d r , is twice the distance between the centers of curvature of O1 and O2 (located on F1), shown as 0.5 d r . The shortest distance between a line parallel to the x axis that includes the center of curvature of O3 (located on F2), and a vertical line that includes the centers of curvature of O1 and O2, is equivalent to the distance between image centers in consecutive columns, and is shown in this figure as d c . The radius of an image on the field mirror is r i . (b) Arrangement of the field images in the modified three objective MMS for a 96 pass system. The locations of the centers of curvature of the objective mirrors, O1–O3, are shown along with d c , d r , and r i .

Fig. 4
Fig. 4

Schematic of the mount used to hold (a) field mirrors F1 and F2 and (b) objective mirrors O1, O2, and O3.

Fig. 5
Fig. 5

Output of a typical ray trace run, with 1 000 000 rays emanating from the FTIR source port for a 2.5   mm aperture and 72 passes. The transfer optics are composed of plane mirrors P1 and P2, and S1, which is the mirror that focuses the beam into the input aperture of the modified three objective MMS. d is the base path length of the cell, and d 2 is the distance from S1 to the MMS input aperture. The distances between the mirrors after the exit aperture are identical to those before the input aperture.

Fig. 6
Fig. 6

(a) Results of measurements of the raw signal at the midband MCT as a function of reflections in the multipass optics. Fitting these results with the expression described in the text allows the average mirror reflectivity over the range 7,500 600 cm - 1 to be determined as 0.98658 ± 0.00024 .

Tables (3)

Tables Icon

Table 1 Comparison of Different Multipass Cell Designs

Tables Icon

Table 2 Dimensions of the Variables for Construction of a Throughput Matched MMS According to Paraxial Equations Eqs. (5)–(8)

Tables Icon

Table 3 Final Optical Specifications of Transfer Optics and Modified Three Objective MMS in HIRAC

Equations (8)

Equations on this page are rendered with MathJax. Learn more.

I I 0 = e σ c l ,
A = In ( I 0 / I ) ( I 0 - I ) / I ,
BD = 2 r 0 + D · AS f ,
Δ ν ˜ best = A S 2 8 f 2 ν ˜ max ,
f 12 = ( r a / α ) ,
d 1 = f 12 ( 1 + r 0 / r b ) ,
d 2 = f 12 ,
1 f 12 = 1 d 1 + 1 ( d 2 + d ) ,

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