Comparison of Infrared-Absorption Intensities of Benzene in the Liquid and Gas Phases

This paper presents a comparison of the absolute infrared absorption intensities in the liquid and gas phases for the four infrared active fundamentals of benzene. In Herzberg’s notation these are ν12 (∼3070 cm−1), and ν4 (∼675 cm−1). Published data are used, including the recently published spectra of liquid benzene that have been accepted by the International Union of Pure and Applied Chemistry as secondary intensity standards. The present results agree qualitatively with the conclusions drawn in 1970 that the intensity Aj of ν12 is much smaller for the liquid than for the gas, and those of ν13, ν14, and ν4 are all larger for the liquid. The inclusion of measurements made since 1970 should make the quantitative results reported here the most reliable. However, two quite different values have been reported in the 1980’s for the intensity of ν14 in the gas phase, and both are considered. The comparison for ν14 is also complicated by the existence of weak bands in the spectrum of the liquid that are not ob...

[1]  Max Born,et al.  Principles of optics - electromagnetic theory of propagation, interference and diffraction of light (7. ed.) , 1999 .

[2]  I. Mills,et al.  Quantities, Units and Symbols in Physical Chemistry , 1993 .

[3]  John E. Bertie,et al.  Infrared Intensities of Liquids XI: Infrared Refractive Indices from 8000 to 2 cm−1, Absolute Integrated Intensities, and Dipole Moment Derivatives of Methanol at 25°C , 1993 .

[4]  Shuliang L. Zhang,et al.  Infrared Intensities of Liquids X: Accuracy of Current Methods of Obtaining Optical Constants from Multiple Attenuated Total Reflection Measurements Using the CIRCLE Cell , 1992 .

[5]  N. Handy,et al.  Higher analytic derivatives. IV. Anharmonic effects in the benzene spectrum , 1992 .

[6]  A. G. Ozkabak,et al.  A benchmark vibrational potential surface : ground-state benzene , 1991 .

[7]  John E. Bertie,et al.  Infrared intensities of liquids. VIII: Accurate baseline correction of transmission spectra of liquids for computation of absolute intensities, and the 1036 cm-1 band of benzene as a potential intensity standard , 1991 .

[8]  A. G. Ozkabak,et al.  The benzene ground state potential surface. IV. Discrimination between multiple E1u force field solutions through infrared intensities , 1989 .

[9]  M. Dignam.  Fourier Transform Polarization Spectroscopy , 1988 .

[10]  R. Jones,et al.  Infrared Intensities of Liquids III: The Photometric Accuracy of FT-IR Transmission Spectra of C5H10, CH3NO2, CH2Cl2, C6H6, C6H5·CH3, and C6H5Cl in the Liquid State at 25°C in 11- to 500-μm Cells , 1986 .

[11]  R. Jones,et al.  Infrared Intensities in Liquids II: Accuracy of FT-IR Transmission Measurements , 1985 .

[12]  J. Bertie,et al.  Infrared Intensities of Liquids I: Determination of Infrared Optical and Dielectric Constants by FT-IR Using the CIRCLE ATR Cell , 1985 .

[13]  M. Wolfsberg,et al.  Dielectric effects on the spectra of condensed phases , 1983 .

[14]  M. Akiyama.  Infrared band intensities and the complete quadratic force field for planar vibrations of gaseous benzene , 1982 .

[15]  M. Akiyama.  Determination of effective-charge distribution on some deuterobenzenes from their out-of-plane gas-band intensities , 1980 .

[16]  R. Jones,et al.  Absolute Absorption Intensity and Dispersion Measurements on Some Organic Liquids in the Infrared , 1980 .

[17]  W. T. King,et al.  Infrared Dispersion in Liquid Benzene and Benzene‐d6 , 1970 .

[18]  H. W. Thompson,et al.  Determination of optical constants and vibrational band intensities of liquids in the infrared using attenuated total reflexion , 1967, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[19]  B. Crawford,et al.  Vibrational Intensities. XIV. The Relation of Optical Constants to Molecular Parameters , 1966 .

[20]  B. Crawford,et al.  Vibrational Intensities. XIII. Reduction of Attenuated Total Reflection Data to Optical Constants , 1966 .

[21]  P. Schatz.  Integration of the Lorentz effective field over an absorption band , 1965 .

[22]  P. Schatz.  Infrared Dispersion Measurements and Integrated Absorption Coefficients for Pure Liquid Benzene , 1960 .

[23]  I. Hisatsune,et al.  Vibrational Intensities of Benzene in the Liquid Phase , 1960 .

[24]  I. Hisatsune,et al.  Vibrational Intensities in Liquid Benzene , 1959 .

[25]  D. Whiffen,et al.  Intensities in the infra-red spectrum of benzene , 1956, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[26]  M. Wilson,et al.  Infrared Intensities in Liquid and Gas Phases , 1955 .

[27]  M. Kakihana,et al.  Charge distribution on benzene determined from infrared band intensities by a new equation , 1989 .

[28]  R. N. Jones,et al.  The determination of the optical constants of benzene and chloroform in the i.r. by thin film transmission , 1976 .

[29]  D. Steele.  The absolute intensities of infrared absorption bands , 1964 .

[30]  M. Davies.  Infra-red spectroscopy and molecular structure : an outline of the principles , 1963 .

[31]  S. Maeda,et al.  REFLECTION SPECTRA AND ABSOLUTE INFRARED INTENSITIES IN PURE $LIQUIDS^{*}$ , 1960 .

[32]  E. Bright Wilson,et al.  Book Reviews: Molecular Vibrations. The Theory of Infrared and Raman Vibrational Spectra , 1955 .