References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-6-2581-2006

The quantitative infrared and NIR spectrum of CH2I2 vapor: vibrational assignments and potential for atmospheric monitoring

Johnson

T. J.

¹ Masiello

¹ Sharpe

S. W.

Pacific Northwest National Laboratory, Richland, WA 99354, USA

04 07 2006

6 9 2581 2591

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/6/2581/2006/acp-6-2581-2006.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/6/2581/2006/acp-6-2581-2006.pdf

Diiodomethane (CH2I2) has recently become a molecule of significant atmospheric interest as it can contribute to coastal IO formation. As part of the PNNL database of gas-phase infrared spectra, the quantitative absorption spectrum of CH2I2 has been acquired at 0.1 cm-1 resolution. Two strong b2 symmetry A-type bands at 584 and 1114 cm-1 are observed, but are not resolved when broadened to 760 Torr with nitrogen and appear as B-type. In contrast, the b1 symmetry C-type bands near 5953, 4426 and 3073 cm-1 are resolved with rotational structure, including Q-branches with widths ≤1 cm-1. The quantitative infrared and near-infrared vapor-phase spectra (600–10 000 cm-1) are reported for the first time. Some bands are discussed in terms of their potential for atmospheric monitoring and theoretical detection limits on a selected basis. FT-Raman spectra and ab initio calculations are used to complete vibrational assignments in the C2v point group.

References 1

Adamiec, P., Salhi, A., Bohdan, R., Bercha, A., Dybala, F., Trzeciakowski, W., Rouillard Y., and Joullié, A.: Pressure-tuned InGaAsSb/AlGaAsSb Diode Laser with 700 nm Tuning Range, Appl. Phys. Lett., 85(19), 4292–4294, 2004.

Alicke, B., Hebestreit, K., Stutz J., and Platt, U.: Iodine Oxide in the Marine Boundary Layer, Nature, 397, 572–573, 1999.

Allen, G., Remedios, J. J., Newnham, D. A., Smith, K. M., and Monks, P. S.: Improved Mid-Infrared Cross-Sections for Peroxyacetyl nitrate (PAN) Vapour, Atmos. Chem. Phys., 5, 47–56, 2005.

Ballard, J., Strong, K., Remedios, J. J., Page, M., and Johnston, W. B.: A Coolable Long Path Absorption Cell for Laboratory Spectroscopic Study of Gases, J. Quant. Spec. Rad. Trans., 52, 677–691, 1994.

Bertie, J. E.: Specification of Components, Methods and Parameters in Fourier Transform Spectroscopy by Michelson and Related Interferometers, Pure Appl. Chem., 70(10), 2039, 1998.

Birk, M., Hausamann, D., Wagner G., and Johns, J. W.: Determination of Line Strengths by Fourier-transform Spectroscopy, Appl. Opt., 35, 2971–2985, 1996.

Bitter, M., Ball, S. M., Povey, I. M., and Jones, R. L.: A Broadband Cavity Ringdown Spectrometer for in situ Measurement of Atmospheric Trace Gases, Atmos. Chem. Phys., 5, 2547–2560, 2005.

Bloss, W. J., Rowley, D. M., Cox, R. A., and Jones, R. L.: Kinetics and Products of the IO Self-reaction, J. Phys. Chem. A., 105, 7840–7854, 2001.

Burkholder, J. B., Curtius, J., Ravishankara A. R., and Lovejoy, E. R.: Laboratory Studies of the Homogeneous Nucleation of Iodine Oxide, Atmos. Chem. Phys., 4, 19–34, 2004.

Carpenter, L. J., Sturges, W. T., Penkett, S. A., Liss, P. S., Alicke, B., Hebestreit, K., and Platt, U.: Short-lived Alkyl Iodides and Bromides at Mace Head, Ireland: Links to Biogenic Sources and Halogen Oxide Production, J. Geophys. Res., 104(D1), 1679–1689, 1999.

Chackerian, C., Sharpe, S. W., and Blake, T. A.: Anhydrous Nitric Acid Integrated Cross Sections: 820–5300 cm$^-1$, J. Quant. Spectr. Rad. Transf., 82(1–4), 429–441, 2003.

Chameides, W. L. and Davis, D. D.: Iodine: Its Possible Role in Tropospheric Photochemistry, J. Geophys. Res., C, 85, 7383–7398, 1980.

Chase, D. B.: Nonlinear Detector Response and FT-IR, Appl. Spec., 38(4), 491–494, 1984.

Chu, P. M., Guenther, F. R., Rhoderick, G. C., and Lafferty, W. J.: The NIST Quantitative Infrared Database, J. Res. Natl. Inst. Stand. Technol., 104, 59, 1999.

Cox, R. A., Bloss, W. J., Jones, R. L., and Rowley, D. M.: OIO and the Atmospheric Cycle of Iodine, Geophys. Res. Lett., 26(13), 1857–1860, 1999.

Evans, W. F. J. and Puckrin, E.: A Wintertime Measurement of the Greenhouse Radiation from Nitrous Oxide, Can. J. Atmos. Sciences and Spectr., 42(5), 141–145, 1997.

Ford, T. A.: Infrared and Raman Spectra and Vibrational Assignments of Diiodomethane and Its Deuterated Analogs, J. Mol. Spec., 58, 185–193, 1975.

Frankenberg, C., Meirink, J. F., van Weele, M., Platt, U., and Wagner, T.: Assessing Methane Emissions from Global Space-Borne Observations, Science, 308, 1010–1014, 2005.

Gilles, M. K., Turnipseed, A. A., Burkholder, J. B., Ravishankara, A. R., and Solomon, S.: Kinetics of the IO radical: 2. Reaction of IO with BrO, J. Phys. Chem. A, 101, 5526–5534, 1997.

Griffith, D. W. T. and Jamie, I. M.: Fourier Transform Infrared Spectrometry in Atmospheric and Trace Gas Analysis, in: Encyclopedia of Analytical Chemistry, edited by: Meyers, R. A., 1979–2000, 2000.

Harwood, M. H., Burkholder, J. B., Hunter, M., Fox, R. W., and Ravishankara, A. R.: Absorption Cross Sections and Self-reaction Kinetics of the IO radical, J. Phys. Chem. A, 101, 853–863, 1997.

Henry, B. R. and Hung, I.-F.: Mass Effects on the Applicability of local Mode Description of the High Energy Overtone Spectra of Difluoro-, Dichloro-, Dibromo- and Diiodomethane, Chem. Phys., 29, 465–475, 1978.

Himmelmann, S., Orphal, J., Bovensmann, H., Richter, A., Ladstätter-Weissenmayer, A., and Burrows, J. P.: First Observation of the OIO Molecule by Time-resolved Flash Photolysis Absorption Spectroscopy, Chem. Phys. Lett., 251, 330–334, 1996.

Hoffmann, T., O'Dowd, C. D., and Seinfeld, J. H.: Iodine oxide homogeneous Nucleation: An Explanation for Coastal New Particle Production, Geophys. Res. Lett., 28(10), 1949–1952, 2001.

Jimenez, J. L., Bahreini, R., Cocker III, D. R., Zhuang, H., Varutbangkul, V., Flagan, R. C., Seinfeld, J. H., O'Dowd, C. D., and Hoffman, T.: New Particle Formation from Photooxidation of Diiodomethane, J. Geophys. Res. D, 108(D10), 4318–4343, 2003.

Johnson, T. J., Roberts, B. A., and Kelly, J. F.: Semiactive Infrared Remote Sensing: A Practical Prototype and Field Comparison, Appl. Opt., 43(3), 638–650, 2004.

Johnson, T. J., Wienhold, F. G., Burrows, J. P., and Harris, G. W.: Frequency Modulation Spectroscopy at 1.3 $\mu $m Using InGaAsP Lasers: A Prototype Field Instrument for Atmospheric Chemistry Research, Appl. Opt., 30, 407–413, 1991a.

Johnson, T. J., Wienhold, F. G., Burrows, J. P., Harris, G. W., and Burkhard, H.: Measurements of Line Strengths in the HO$_2 ~ \nu _1$ Overtone Band at 1.5 $\mu $m Using an InGaAsP Laser, J. Phys. Chem., 95, 6499–6502, 1991b.

Johnson, T. J., Valentine, N. B., and Sharpe, S. W.: Mid-infrared versus Far-infrared (THz) Relative Intensities of Room-temperature \textitBacillus spores, Chem. Phys. Lett., 403, 152–157, 2005.

Johnson, T. J., Sams, R. L., Blake, T. A., Sharpe, S. W., and Chu, P. M.: Removing Aperture-Induced Artifacts from FTIR Intensity Values, Appl. Opt., 41, 2831–2839, 2002.

Johnson, T. J., Disselkamp, R. S., Su, Y.-F., Fellows, R. J., Alexander, M. L. and Driver, C. L.: Gas-phase Hydrolysis of SOCl$_2$: Implications for Its Atmospheric Fate, J. Phys. Chem. A, 107, 6183–6190, 2003.

Kasper, J. V. V., Parker, J. H., and Pimentel, G. C.: Atomic Iodine Photodissociation Laser, Appl. Phys. Lett., 5(11), 231–233, 1964.

Kasper, J. V. V., Parker J. H., and Pimentel, G. C.: Iodine-Atom Laser Emission in Alkyl Iodine Photolysis, J. Chem. Phys., 43, 1827–1828, 1965.

Kendall, R. A., Apra, E., Bernholdt, D. E., Bylaska, E. J., Dupuis, M., Fann, G. I., Harrison, R. J., Ju, J., Nichols, J. A., Nieplocha, J., Straatsma, T. P., Windus, T. L., and Wong, A. T.: High Performance Computational Chemistry: An Overview of NWChem, a Distributed Parallel Application, Computer Phys. Comm., 128, 260–283, 2000.

Kolb, C. E.: Iodine's Air of Importance, Nature, 417, 597–598, 2002.

Kroger, P. M., Demou, P. C., and Riley, S. J.: Polyhalide Photofragment Spectra. I. Two-photon Two-step Photodissociation of Methylene Iodide, J. Chem. Phys., 65(5), 1823–1834, 1976.

Mäkelä, J. M., Hoffmann, T., Holzke, C., Väkevä, M., Suni, T., Mattila, T., Aalto, P. P., Tapper, U., Kauppinen, E. I., and O'Dowd, C. D.: Biogenic Iodine Emissions and Identification of End-products in Coastal Ultrafine Particles during Nucleation Bursts, J. Geophys. Res., 107(D19), 8110–8124, 2002.

Maki, A., Blake, T. A., Sams, R. L., Vulpanovici, N., Barber, J., Chrysostom, E. T. H., Masiello, T., Nibler, J. W., and Weber, A.: High Resolution Infrared Spectra of the $\nu _2$, $\nu _3$, $\nu _4$, and 2$\nu _3$ bands of $^32$S$^16$O$_3$, J. Mol. Spectrosc., 210, 240–249, 2001.

Maki, A. G. and Wells, J. S.: Wavenumber Calibration Tables from Heterodyne Frequency Measurements, NIST Special Publication 821, National Institute of Standards and Technology, U.S. Government Printing Office, Washington, D.C., 1991.

Marshall, P., Srinivas, G. N., and Schwartz, M.: A Computational Study of the Thermochemistry of Bromine- and Iodine-Containing Methanes and Methyl Radicals, J. Phys. Chem. A, 109, 6371, 2005.

Masiello, T., Maki, A., and Blake, T. A.: The High-resolution Infrared Spectrum of $^11$BF$_3$ from 400 to 1650 cm$^-1$, J. Mol. Spectrosc., 234, 122–136, 2005.

McFiggans, G., Coe, H., Burgess, R., Allen, J., Cubison, M., Alfarra, M. R., Saunders, R., Saiz-Lopez, A., Plane, J. M. C., Wevill, D. J., Carpenter, L. J., Rickard, A. R., and Monks, P. S.: Direct Evidence for Coastal Iodine Particles from Laminaria Macroalgae – Linkage to Emissions of Molecular Iodine, Atmos. Chem. Phys. 4, 701–713, 2004.

Mertz, L.: Auxiliary Computation for Fourier Spectrometry, Infr. Phys., 7, 17, 1967.

Orphal, J. and Ibrahim, N.: The $\nu _1$ and $\nu _6$ Bands of Diiodomethane, CH$_2$I$_2$, around 3.3. Microns Studied by High-Resolution Fourier-Transform Spectroscopy, in: 19th Colloquium on High Resolution Molecular Spectroscopy, Salamanca, Spain, 11–16 September 2005.

Platt, U.: Differential Optical Absorption Spectroscopy, in: Monitoring by Spectroscopic Techniques, edited by: Sigrist, M. W., chapter 2, 27–84, Wiley & Sons, New York, 1994.

Platt, U., Perner, D., Harris, G. W., Winer, A. M., and Pitts, J. N.: Observations of Nitrous Acid in an Urban Atmosphere by Differential Optical-Absorption, Nature, 285, 312–314, 1980.

Richter, D., Fried, A., Wert, B. P., Walega, J. G., and Tittel, F. K.: Development of a Tunable mid-IR Difference Frequency Laser Source for Highly Sensitive Airborne Trace Gas Detection, Appl. Phys. B, 75, 281–288, 2002.

Rothman, L. S., Jacquemart, D., Barbe, A., Brenner, D. C., et al.: The HITRAN 2004 Molecular Spectroscopic Database, J. Quant. Spectrosc. Rad. Transf., 96, 139–204, 2005.

Rowley, D. M., Bloss, W. J., Cox, R. A., and Jones, R. L.: Kinetics and Products of the IO+BrO Reaction, J. Phys. Chem. A, 105, 7855–7864, 2001.

Schiller, C. L., Locquiao, S., Johnson, T. J., and Harris, G. W.: Atmospheric Measurements of HONO by Tunable Diode Laser Absorption Spectroscopy, J. Atmos. Chem., 40, 275–293, 2001.

Schmitt, G. and Comes, F. J.: Spectroscopic Investigations of the Photolysis of Diiodomethane, J. Mol. Struct., 61, 51–54, 1980.

Sharpe, S. W., Kelly, J. F., Hartman, J. S., Gmachl, C., Capasso, F., Sivco, D. L., Baillargeon, J. N., and Cho, A. Y.: High-resolution (Doppler-limited) Spectroscopy Using Quantum-cascade Distributed-feedback Lasers, Opt. Lett., 23(17), 1396–1398, 1998.

Sharpe, S. W., Johnson, T. J., Chu, P. M., Kleimeyer, J., and Rowland, B.: Quantitative Infrared Spectra of Vapor Phase Chemical Agents, SPIE Proceedings, 5058, 19–27, 2003.

Sharpe, S. W., Johnson, T. J., Sams, R. L., Chu, P. M., Rhoderick, G. C., and Johnson, P. A.: Gas-phase Databases for Quantitative Infrared Spectroscopy, Appl. Spectr., 58(12), 1452–1461, 2004.

Solomon, S., Garcia, R. R., and Ravishankara, A. R.: On the Role of Iodine in Ozone Depletion, J. Geophys. Res., 99(D10), 20 491–20 499, 1994.

Tucceri, M. E., Hölscher, D., Rodriguez, A., Dillon, T. J., and Crowley, J. N.: Absorption cross section and photolysis of OIO, Phys. Chem. Chem. Phys., 8, 834–846, 2006.

Voelz, F. L., Cleveland, F., Meister, A. G., and Bernstein, R. B.: Substituted Methanes. XVII: Vibrational Spectra, Potential Constants, and Calculated Thermodynamic Properties of Diiodomethane, J. Opt. Soc. Am., 43, 1061–1064, 1953.

Vogt, R., Sander, R., von Glasow, R., and Crutzen, P. J.: Iodine Chemistry and Its Role in Halogen Activation and Ozone Loss in the Marine Boundary Layer, J. Atmos. Chem., 32, 375–395, 1999.

Volkamer, R., Molina, L. T., Molina, M. J., Shirley, T., and Brune, W. H.: DOAS Measurement of Glyoxal as an Indicator for Fast VOC Chemistry in Urban Air, Geophys. Res. Lett., 32, L08806, doi:10.1029/2005GL022616, 2005.

Warneck, P.: Chemistry of the Natural Atmosphere, p. 146 ff. Academic Press, San Diego, 1988.

Werle, P. W., Mazzinghi, P., D'Amato, F., De Rosa, M., Maurer, K., and Slemr, F.: Signal Processing and Calibration Procedures for in situ Diode-laser Absorption Spectroscopy, Spectrochimica Acta A, 60, 1685–1705, 2004.

Wert, B. P., Fried, A., Rauenbuehler, S., Walega, J., and Henry, B.: Design and Performance of a Tunable Diode Laser Absorption Spectrometer for Airborne Formaldehyde Measurements, J. Geophys. Res., 108(D12), 4350–4362, 2003.

Wevill, D. J. and Carpenter, L. J.: Automated Measurement and Calibration of Reactive Volatile Halogenated Organic Compounds in the Atmosphere, Analyst, 129, 634–638, 2004.

Williams, S. D., Johnson, T. J., Gibbons, T. P., and Kitchens, C. L.: Relative Raman Intensities in C$_6$H$_6$, C$_6$D$_6$, and C$_6$F$_6$: a Comparison of Different Computational Methods, Theo. Chem. Acc., in press, 2006.

Yaws, C. L.: Chemical Properties Handbook, McGraw-Hill, New York, 1999.