Light-Induced Mid-Infrared Emission of Liquid Carbon Tetrachloride and Benzene


Light-induced infrared emission spectroscopy (LIRES) is a novel technique that permits to receive high-quality spectra in the mid-infrared region. Low-intensity visible light connected to a highly sensitive FTIR spectrometer is more advantageous for studying any samples, including biological samples without any damage. This technique permits obtaining unique information on the molecule structure via vibrational excitation fundamental frequencies, overtones, and combination modes. It also enables a direct observation of vibrational radiation transitions in vibrationally excited molecules as well as the channels of vibration energy redistribution, which is not allowed with any other method. In this work, the LIRES is being tested as a technique for studying of vibrationally-excited molecules of carbon tetrachloride and benzene in the liquid phase. On the other hand, using transparent liquids, we had tried to understand some of the physical phenomena that can drive emission in mid-IR. The characteristics of the infrared emission of both liquid species produced by different wavelength radiation from various types of light systems (100 - watt Xe-lamp and Nd:YAG laser; lambda = 1064 nm (8 mW) and lambda = 532 nm (4 mW)) are presented. We demonstrated that the IR-signal, as well as spectral properties of carbon tetrachloride and benzene, was dependent on the wavelength and power of excitation beam. Results obtained with different light sources show that the visible light produces a nonlinear IR-emission signal in transparent liquids. We believe that the visible light is the source of the nonlinear response and is producing the vibration excitation as well as photostimulated transformations of the molecules possessing the high activity for the nonlinear response.

Share and Cite:

Terpugova, S. , Degtyareva, O. , Savransky, V. and Terpugov, E. (2015) Light-Induced Mid-Infrared Emission of Liquid Carbon Tetrachloride and Benzene. American Journal of Analytical Chemistry, 6, 731-745. doi: 10.4236/ajac.2015.69070.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] De Blasé, F.J. and Compton, S. (1991) Infrared Emission Spectroscopy: A Theoretical and Experimental Review. Applied Spectroscopy, 45, 611-618.
[2] Mink, J. and Keresztury, G. (1993) FT-IR Emission Spectroscopy and Its Applications. Applied Spectroscopy, 47, 1446-1451.
[3] Chalmers, J.M. and Mackenzie, M.W. (1988) Emission Spectroscopy. In: Mackenzie, M.W., Ed., Advances in Applied Fourier Transform Infrared Spectroscopy, Wiley & Sons, Ltd., Chichester and New York, 170-188.
[4] Griffiths, P.R. (1975) Chemical Infrared Fourier Transform Spectroscopy. Wiley-Interscience, New York.
[5] Theophanides, T.M., Ed. (1984) Fourier Transform Infrared Spectroscopy: Industrial Chemical and Biochemical Applications. D. Reidel Publishing Co., Dodrecht.
[6] Griffiths, P.R. and de Haseth, J.A. (1986) Fourier Transform Infrared Spectrometry. Wiley-Interscience, New York.
[7] Moehlmann, J.G., Gleaves, J.T., Hudgens, J.W. and McDonald, J.D. (1974) Infrared Chemiluminescence Studies of the Reaction of Fluorine Atoms with Monosubstituted Ethylene Compounds. The Journal of Chemical Physics, 60, 4790-4799.
[8] Cook, D.J., Schlemmer, S., Balucani, N., Wagner, D.R., Harrison, J.A., Steiner, B. and Saykally, R.J. (1998) Single Photon Infrared Emission Spectroscopy: A Study of IR Emission from UV Laser Excited PAHs between 3 and 15 μm. Journal of Physical Chemistry A, 102, 1465-1481.
[9] Lin, L.T., Archibald, D.D. and Honigs, D.E. (1988) Preliminary Studies of Laser-Induces Thermal Emission Spectroscopy of Condensed Phases. Applied Spectroscopy, 42, 477-483.
[10] Tsuge, A., Uwamino, Y. and Ishizuka, T. (1989) Applications of Laser-Induces Thermal Emission Spectroscopy to Various Samples. Applied Spectroscopy, 43, 1145-1149.
[11] Hailey, D.M., Barnes, H.M., Woodward, C. and Robinson, J.W. (1971) A Catalog of Laser-Stimulated Infrared Emission Spectra. Analytica Chimica Acta, 56, 161-174.
[12] Hailey, D.M., Barnes, H.M. and Robinson, J.W. (1971) Infrared Fluorescence Spectroscopy as an Analytical Method: Quantitative Studies with a Long Pathlength Cell. Analytica Chimica Acta, 56, 175-183.
[13] Robinson, J.W. and Dake, J.D. (1974) Remote Sensing of Air Pollutants by Laser-Induced Fluorescence—A Review. Analytica Chimica Acta, 71, 277-288.
[14] Robinson, J.W., Hailey, D.M. and Barnes, H.M. (1969) Infrared Emission of Organic Compounds Stimulated by a Laser Beam. Talanta, 16, 1109-1111.
[15] Terpugov, E.L. and Degtyareva, O.V. (1997) IR-Emission of Bacteriorhodopsin under Visible Light Excitation. 11th International Conference on Fourier Transform Infrared Spectroscopy, Book of Abstract M. 26.
Terpugov, E.L. and Degtyareva, O.V. (2001) Infrared Emission from Photoexcited Bacteriorhodopsin: Studies by Fourier Transform Infrared Spectroscopy. Journal of Molecular Structure, 565-566, 287-292.
Terpugov, E.L. and Degtyareva, O.V. (2001) FTIR Emission Spectra of Bacteriorhodopsin in a Vibrational Excited State. Biochemistry, 66, 1628-1637.
[16] Terpugov, E.L. and Degtyareva, O.V. (2000) Investigation of Thin Films Using Fourier Transform Infrared Emission Spectroscopy. Proceedings of SPIE, 4129, 659-663.
[17] Terpugov, E.L. and Degtyareva, O.V. (2001) Lysine IR-Emission Spectrum Excited by Moderately Intense Visible Radiation. Journal of Experimental and Theoretical Physics Letters, 73, 320-323.
[18] Gorelik, V.S., Gagrinov, A.G., Degtyareva, O.V., Savranskii, V.V. and Terpugov, E.L. (2006) Infrared Emission of Single-Cryctal Calcite under Broadband Short-Wavelength Excitation. Inorganic Materials, 42, 1251-1254.
[19] Gagarinov, A.G., Degtyareva, O.V., Khodonov, A.A. and Terpugov, E.L. (2006) Stimulated Infrared Emission All-Trans Retinal and Wild-Type Bacteriorhodopsin under CW Optical Pumping: Studies by FT-IR Spectroscopy. Vibrational Spectroscopy, 42, 231-238.
[20] Terpugov, E.L., Degtyareva, O.V., Gagarinov, A.G. and Savransky, V.V. (2004) Genaration of IR-Emission in Biological Films under Broad-Band Pumping. Bulletin of the Lebedev Physics Insitute (P.N. Lebede Physics Institute of the Russian Academy of sciences) (Russian), 12, 13-22.
[21] Balashov, A.A., Vaguine, V.A., Viskovatich, A.V., Grishkovski, B., Lazarev, Y.A. and Terpugov, E. (1991) Two- Channel Fourier Spectrometer for Biophysical Studies. Proceedings of SPIE, 1575, 182-183.
[22] Reddy, K.V, Heller, D.F. and Berry, M.J. (1982) Highly Vibrationally Excited Benzene: Overtone Spectroscopy and Intramolecular Dynamics of C6H6, C6D6, and Partially Deuterated or Substituted Benzenes. The Journal of Chemical Physics, 76, 2814-2837.
[23] Tyson, D.G. and Jennings, B.R. (1991) Measurement of the “Optical” Kerr Effect Induces by Nanosecond Laser Pulses. Journal of Physics D: Applied Physics, 24, 645-653.
[24] Chiao, R.Y., Garmie, E. and Townes, C.H. (1964) Self-Trapping of Optical Beam. Physical Review Letters, 13, 479-482.
[25] Bloembergen, N. (1965) Nonlinear Optics. W.A. Benjamin Inc., New York.
[26] Akhmanov, S.A. and Khokhlov, R.V. (1964) Problems of Nonlinear Optics. Nauka Publishers, Moscow.
[27] Shen, Y.R. (1984) The Principles of Nonlinear Optics. John Wiley & Sons, New York.
[28] Pilipetskii, N.F. and Rustamov, A.R. (1965) Observation of Self-Focusing of Light in Liquids. Journal of Experimental and Theoretical Physics Letters, 2, 55-56.
[29] Talanov, V.I. (1970) About Self-Focusing of Light in Cubic Media. Journal of Experimental and Theoretical Physics Letters, 11, 199-201.
[30] Kelley, P.L. (1965) Self-Focusing of Optical Beams. Physical Review Letters, 15, 1005-1008.
[31] Alfano, R.R. and Shapiro, S.L. (1970) Observation of Self-Phase Modulation and Small-Scale Filaments in Crystals and Glasses. Physical Review Letters, 24, 592-594.
[32] Boyd, R.W., Lukishova, S.G. and Shen, Y.R. (Eds.) (2009) Self-Focusing: Past and Present Fundamentals and Prospects. Springer Science+Business Media, New York.
[33] Bjorkholm, J.E. and Ashkin, A.A. (1974) Cw Self-Focusing and Self-Trapping of Light in Sodium Vapour. Physical Review Letters, 32, 129-132.
[34] Braun, E., Faucheux, L.P. and Libchaber, A. (1993) Strong Self-Focusing in Nematic Liquid. Physical Review A, 48, 611-622.
[35] Tabiryan, N.V., Sukhov, A.V. and Zel’dovich, B.YA. (1986) Orientational Optical Nonlinearity of Liquid Crystals. Molecular Crystals and Liquid Crystals, 136, 1-139.
[36] Etchegoin, P. and Phillips, R.T. (1996) Stimulated Raman Scattering Produced by Self-Focusing in Liquid Crystals. Physical Review E, 54, 2637-2646.
[37] Leite, R.C.C., Moore, R.S. and Whinnery, J.R. (1964) Low Absorption Measurement by Means of the Thermal Lens Effect Using an He-Ne Laser. Applied Physics Letters, 5, 141-143.
[38] Gordon, J.P., Leite, R.C.C., Moore, R.S., Porto, S.P.S. and Whinnery, J.R. (1965) Long-Transient Effects in Lasers with Inserted Liquid Samples. Journal of Applied Physics, 36, 3-8.
[39] Dovichi, N.J. and Harris, J.M. (1979) Laser-Induced Thermal Lens Effect for Calorimetric Trace-Analysis. Analytical Chemistry, 51, 728-731.
[40] Hu, C. and Winnery, J.R. (1973) New Thermooptical Measurement Method and a Comparison with Other Methods. Applied Optics, 12, 72-79.
[41] Lallemand, P. and Bloembergen, N. (1965) Self-Focusing of Laser Beams and Stimulated Raman Gain in Liquids. Physical Review Letters, 15, 1010-1012.
[42] Chiao, R.Y., Garmire, E., Johnson, M.A., Krinsky, S., Smith, H.A. and Townes, C.H. (1966) A New Class of Trapped Light Filaments. IEEE Journal of Quantum Electronics, 2, 467-469.
[43] Akhmanov, S.A., Sukhorukov, A.P. and Khokhlov, R.V. (1968) Self-Focusing and Difraction of Light in a Nonlinear Medium. Uspekhi Fizicheskikh Nauk, 10, 609-636.
[44] Chiao, R.Y., Gustafson, T.K. and Kelley, P.L. (2009) Self-Focusing of Optical Beam, Self-Focusing: Past and Present. In: Boyd, R.W., Lukishova, S.G. and Shen, Y.R., Eds., Topics in Applied Physics, Vol. 114, Springer Science+Business Media, LLC, New York, 129-143.
[45] De Martini, F. (1966) Theory of the Infrared Generation by Coherently Driven Molecular Vibrations. Journal of Applied Physics, 37, 4503-4507.
[46] Gorelik, V.S., Zubov, V.A., Suschinski, M.M. and Chirov, V.A. (1966) About Possibility the Generation of Infrared Emission Concurrent Raman Scattering. Journal of Experimental and Theoretical Physics Letters, 4, 252-254.
[47] Tannenwald, P.E. and Weinberg, D.L. (1967) Stimulated Raman Scattering in an Infrareds Active, Nontotally Symmetric Vibration of λ-Quartz. IEEE Journal of Quantum Electronics, 3, 334-335.
[48] Herzberg, G. (1945) Molecular Spectra and Molecular Structure. Part II. Infrared and Raman Spectra of Polyatomic Molecules. Van Nostrand Comp., New York.
[49] Moskovits, M., DiLella, D.P. and Maynard, K.J. (1988) Surface Raman Spectroscopy of a Number of Cyclic Aromatic Molecules Adsorbed on Silver: Selection Rules and Molecular Orientation. Langmuir, 4, 67-76.
[50] Goodman, L., Ozkabak, A.G. and Thakur, S.N. (1991) A Benchmark Vibrational Potential Surface: Ground-State Benzene. The Journal of Physical Chemistry, 95, 9044-9058.
[51] Lin-Vien, D., Colthup, N.B., Fateley, W.G. and Grasselli, J.G. (1991) The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules. Chap. 17, Academic Press, Inc., San-Diego.
[52] The Vibrations of Benzene Have Been the Subject of Intense Investigations as Summerized in Ref. [49] and Following Works:
Sibert, E.L., Reinhardt, W.P. and Hynes, J.T. (1984) Intramolecular Vibrational Relaxation and Spectra of CH and CD Overtones in Benzene and Perdeuterobenzene. The Journal of Chemical Physics, 81, 1115-1134.
Thakur, S.N., Goodman, L. and Ozkabak, A.G. (1986) The Benzene Ground State Potential Surface. I. Fundamental Frequencies for the Planar Vibrations. The Journal of Chemical Physics, 84, 6642-6655.
Goodman, L., Berman, J.M. and Ozkabak, A.G. (1989) The Benzene Ground State Potential Surface. III. Analysis of b2u Vibrational Mode Anharmonicity through Two-Photon Intensity. The Journal of Chemical Physics, 90, 2544-2554.
Page, R.H., Shen, Y.R. and Lee, Y.T. (1988) Infrared-Ultraviolet Double Resonance Studies of Benzene Molecules in a Supersonic Beam. The Journal of Chemical Physics, 88, 5362-5376.
Ozkabak, A.G., Goodman, L. and Thakur, S.N. (1991) A Benchmark Vibrational Potential Surface: Ground-State Benzene. The Journal of Chemical Physics, 95, 9044-9058.
Christiansen, O., Stanton, J.F. and Gauss, J. (1998) A Coupled Cluster Study of the 11A1g and 11B2u States of Benzene. The Journal of Chemical Physics, 108, 3987-4001.
Senent, M.-L., Palmieri, P., Carter, S. and Handy, N.C. (2002) The Vibrations of Benzene, Studied by “Multimode”. Chemical Physics Letters, 354, 1-8.
[53] Sur, A., Knee, J. and Johnson, P. (1982) The 1B2u←←1Alg Two-Photon Spectra of Several Isotopes of Benzene by Supersonic Beam-Multiphoton Ionization Spectroscopy. The Journal of Chemical Physics, 77, 654-669.
[54] Acker, W.P., Leach, D.H. and Chang, R.K. (1989) Stokes and Anti-Stokes Hyper-Raman Scattering from Benzene, Deuterated Benzene, and Carbon Tetrachloride. Chemical Physics Letters, 155, 491-495.
[55] Plíva, J., Johns, J.W.C. and Lu, Z. (1996) The Difference Bands v11-v4 and v10-v18 of Benzene at High Resolution. Molecular Physics, 87, 859-863.

Copyright © 2023 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.