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Far-infrared spectra and associated dynamics in acetonitrile–water mixtures measured with femtosecond THz pulse spectroscopy

J. Chem. Phys. 108, 4935 (1998); doi:10.1063/1.475902

Issue Date: 22 March 1998

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D. S. Venables and C. A. Schmuttenmaer
Department of Chemistry, Yale University, 225 Prospect St., New Haven, Connecticut 06520-8107
We report the frequency-dependent absorption coefficient and index of refraction in the far-infrared region of the spectrum for mixtures of acetonitrile and water. The mixtures do not behave ideally, and deviate from ideality most noticeably for mixtures that are between 25% and 65% acetonitrile by volume. Two implementations of the Debye model for describing the dielectric relaxation behavior of mixtures are compared, and we show that these mixtures are better treated as uniform solutions rather than as two-component systems. We find an enhanced structure in the mixtures, relative to ideal mixtures, but we do not find direct evidence for microheterogeneity. The Debye time constant for the primary relaxation process for the mixtures is up to 25% longer than that for an ideal mixture. ©1998 American Institute of Physics.
History: Received 4 November 1997; accepted 22 December 1997
Permalink: http://link.aip.org/link/?JCPSA6/108/4935/1
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KEYWORDS and PACS

Keywords
PACS
  • 78.30.Cp
    Optical properties, condensed-matter spectroscopy and other interactions of radiation and particles with condensed matter Infrared and Raman spectra Liquids
  • 78.20.Ci
    Optical properties, condensed-matter spectroscopy and other interactions of radiation and particles with condensed matter Optical properties of bulk materials and thin films Optical constants: refractive index, complex dielectric constant, absorption, reflection and transmission coefficients, emissivity
  • 78.47.+p
    Optical properties, condensed-matter spectroscopy and other interactions of radiation and particles with condensed matter Time-resolved optical spectroscopies and other ultrafast optical measurements in condensed matter
  • 64.75.+g
    Equations of state, phase equilibria, and phase transitions Solubility, segregation, and mixing; phase separation
  • 77.22.Gm
    Dielectrics, piezoelectrics, and ferroelectrics and their properties Dielectric properties of solids and liquids Dielectric loss and relaxation
  • YEAR: 1998

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (65)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. I. Rips, J. Klafter, and J. Jortner, J. Chem. Phys. 88, 3246 (1988).
  2. F. O. Raineri, H. Resat, B. C. Perng, F. Hirata, and H. L. Friedman, J. Chem. Phys. 100, 1477 (1994).
  3. B. Bagchi and A. Chandra, Adv. Chem. Phys. 80, 1 (1991).
  4. M. Maroncelli, J. Mol. Liq. 57, 1 (1993).
  5. R. A. Marcus, Pure Appl. Chem. 69, 13 (1997).
  6. Z. B. Alfassi, R. E. Huie, and P. Neta, J. Phys. Chem. 97, 7253 (1993).
  7. I. H. Um, G. J. Lee, H. W. Yoon, and D. S. Kwon, Tet. Lett. 33, 2023 (1992).
  8. P. Vöhringer and N. F. Scherer, J. Phys. Chem. 99, 2684 (1995).
  9. Y. J. Chang and E. W. Castner, Jr., J. Phys. Chem. 100, 3330 (1996).
  10. S. Kinoshita, Y. Kai, M. Yamaguchi, and T. Yagi, Phys. Rev. Lett. 75, 148 (1995).
  11. S. Palese, J. T. Buontempo, L. Schilling, W. T. Lotshaw, Y. Tanimura, S. Mukamel, and R. J. D. Miller, J. Phys. Chem. 98, 12 466 (1994).
  12. T. Lian, Y. Kholodenko, and R. M. Hochstrasser, J. Phys. Chem. 99, 2546 (1995).
  13. M. Cho, M. Du, N. F. Scherer, G. R. Fleming, and S. Mukamel, J. Chem. Phys. 99, 2410 (1993).
  14. J. Barthel and R. Buchner, Pure Appl. Chem. 63, 1473 (1991).
  15. E. Knözinger, D. Leutloff, and R. Wittenbeck, J. Mol. Struct. 60, 115 (1980).
  16. T. Tassaing, Y. Danten, M. Besnard, E. Zoidis, J. Yarwood, Y. Guissani, and B. Guillot, Mol. Phys. 84, 769 (1995).
  17. Y. C. Guillaume and C. Guinchard, Anal. Chem. 69, 183 (1997).
  18. D. A. Armitage, M. J. Blandamer, M. J. Foster, N. J. Hidden, K. W. Morcom, M. C. R. Symons, and M. J. Wooten, Trans. Faraday Soc. 67, 1193 (1968).
  19. The Napierian power absorption coefficient, alpha, is based on Beer's law: P/P0 = e–alphad, where P0 is incident power, P is transmitted power, and d is the sample thickness in cm. Upon rearrangement, we find alpha = [ln(P/P0)]/d, and this is the quantity plotted in Figs. 3 and 4. Unfortunately, alpha is often incorrectly reported with units of "neper/cm," which can cause confusion. One neper (1 Np) is the level of a field, or amplitude, quantity when F/F0 = e (where e is the base of natural logarithms) or equivalently, ln(F/F0) = 1.20 Therefore, it is the level of a power, or intensity, quantity when P/P0 = e2, or ln(P/P0) = 2, not when ln(P/P0) = 1, as is often incorrectly assumed.
  20. B. N. Taylor, Guide for the Use of the International System of Units (SI), NIST Special Publication 811, 1995 edition (U.S. Government Printing Office, Washington, DC, 1995).
  21. T. Ohba and S. Ikawa, Mol. Phys. 73, 985 (1991).
  22. J. E. Bertie and Z. D. Lan, Appl. Spectrosc. 50, 1047 (1996).
  23. H. S. Frank and M. W. Evans, J. Chem. Phys. 13, 507 (1945).
  24. Y. I. Naberukhin and A. Rogov, Russ. Chem. Rev. 40, 297 (1971).
  25. H. T. French, J. Chem. Thermodyn. 19, 1155 (1987);
    26. K. W. Morcom and R. W. Smith, 1, 503 (1969).
  26. C. Moreau and Douhéret, Thermochim. Acta 13, 385 (1975).
  27. C. Moreau and Douhéret, J. Chem. Thermodyn. 8, 403 (1976).
  28. F. Mato and J. L. Hernandez, An. Quim. 65, 9 (1969).
  29. M. I. Davis, Thermochim. Acta 63, 67 (1983).
  30. A. J. Easteal, Aust. J. Chem. 33, 1667 (1980).
  31. M. I. Davis, Thermochim. Acta 73, 149 (1984).
  32. C. de Visser, W. J. M. Heuvelsland, L. A. Dunn, and G. Somsen, J. Chem. Soc., Faraday Trans. 74, 1159 (1978).
  33. E. Matteoli and L. Lepori, J. Chem. Phys. 80, 2856 (1984).
  34. M. I. Davis, Thermochim. Acta 71, 59 (1983).
  35. M. I. Davis and G. Douhéret, Thermochim. Acta 104, 203 (1986).
  36. Y. Marcus and Y. Migron, J. Phys. Chem. 95, 400 (1991).
  37. G. Eaton, A. S. Pena-Nuñez, and M. C. R. Symons, J. Chem. Soc., Faraday Trans. 84, 2181 (1988).
  38. G. Eaton, A. S. Pena-Nuñez, M. C. R. Symons, M. Ferrario, and I. R. McDonald, J. Chem. Soc., Faraday Trans. 85, 237 (1988).
  39. D. Jamroz, J. Stangret, and J. Lindgren, J. Am. Chem. Soc. 115, 6165 (1993).
  40. J. E. Bertie and Z. Lan, J. Phys. Chem. 101, 4111 (1997).
  41. K. L. Rowlen and J. M. Harris, Anal. Chem. 63, 964 (1991).
  42. M. Stoev, A. Makarow, and J. M. A. Robledo, Spectrosc. Lett. 28, 1251 (1995).
  43. E. v. Goldammer and H. G. Hertz, J. Phys. Chem. 74, 3734 (1970).
  44. J. R. Damewood and R. A. Kumpf, J. Phys. Chem. 91, 3449 (1987).
  45. P. I. Nagy, Acta Chim. Hungary 129, 429 (1992).
  46. K. Nakanishi, Chem. Soc. Rev. X, 177 (1993).
  47. H. Kovacs and A. Laaksonen, J. Am. Chem. Soc. 113, 5596 (1991).
  48. E. Hawlicka, Polish J. Chem. 70, 821 (1996).
  49. H. Kovacs and A. Laaksonen, J. Am. Chem. Soc. 113, 5596 (1991).
  50. E. Hawlicka, Polish J. Chem. 70, 821 (1996).
  51. X.-C. Zhang, B. B. Hu, J. T. Darrow, and D. H. Auston, Appl. Phys. Lett. 56, 1011 (1990);
    52. N. Katzenellenbogen and D. Grischkowsky, 58, 222 (1991).
  52. J. T. Kindt and C. A. Schmuttenmaer, J. Phys. Chem. 100, 10 373 (1996).
  53. S. R. Keiding, J. Phys. Chem. 101, 5250 (1997).
  54. C. Rønne, L. Thrane, P. O. Åstrand, A. Wallqvist, K. V. Mikkelsen, and S. R. Keiding, J. Chem. Phys. 107, 5319 (1997).
  55. B. N. Flanders, R. A. Cheville, D. Grischkowsky, and N. F. Scherer, J. Phys. Chem. 100, 11824 (1996).
  56. Y. Y. Akhadov, Dielectric Properties of Binary Solutions (Pergamon, New York, 1980).
  57. T. Tassaing, Y. Danten, M. Besnard, E. Zoïdis, and J. Yarwood, Chem. Phys. 184, 225 (1994).
  58. H. Wode and W. Seidel, Ber. Bunsenges. Phys. Chem. 98, 927 (1994).
  59. P. Turq, J. Barthel, and M. Chemla, Transport, Relaxation, and Kinetic Processes in Electrolyte Solutions (Springer-Verlag, New York, 1992).
  60. P. Kedziora, J. Jadzyn, and P. Bonnet, Ber. Bunsenges. Phys. Chem. 97, 864 (1993).
  61. Water: A Comprehensive Teatise, edited by F. Franks, (Plenum, New York, 1972), Vol. 1.
  62. K. Mizoguchi, Y. Hori, and Y. Tominaga, J. Chem. Phys. 97, 1961 (1992).
  63. G. E. Walrafen, M. S. Hokmabadi, W. H. Yang, Y. C. Chu, and B. Monosmith, J. Phys. Chem. 93, 2909 (1989).
  64. H. R. Zelsmann, J. Mol. Struct. 350, 95 (1995).
  65. U. Kaatze, J. Chem. Eng. Data 34, 371 (1989).

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