High pressure solid phases of benzene. I. Raman and x‐ray studies of C6H6 at 294 K up to 25 GPa

Crystalline benzene has been investigated at room temperature as a function of pressure up to 25 GPa in diamond anvil cells by Raman scattering and powder x‐ray diffraction techniques. The concomitant spectroscopic and crystallographic results show the existence of numerous pressure‐induced phases. Changes in the profiles of the Raman spectra and in the x‐ray diffraction patterns, as well as changes in the variations of the Raman frequencies and the cell parameters with pressure indicate two first‐order phase transitions at 1.4±0.1 and 4±1 GPa and a second‐order one at 11±1 GPa. At 24 GPa the x‐ray diffraction pattern seems to indicate the existence of a new phase. Two monoclinic structures are proposed for the phases above 1.5 GPa, in addition to the already known one. From these data, molar volume has been determined as a function of pressure and the Gruneisen parameters have been inferred in the different phases. Their pressure dependences are analyzed in the light of theoretical predictions. Arguments are given for a phase transformation at normal pressure and below 140 K or at room temperature below 1 GPa. A schematic P–T phase diagram is suggested and a controversy on the nature of the triple points located on the melting curve is clarified.

[1]  S. Zwerdling,et al.  Motions of Molecules in Condensed Systems. IX. Infrared Absorption Anisotropy and Induced Molecular Motion in a Single Crystal of Benzene , 1955 .

[2]  R. Zallen,et al.  Influence of pressure and temperature on phonons in molecular chalcogenides: Crystalline As 4 S 4 and S 4 N 4 , 1978 .

[3]  K. Kobashi,et al.  Raman spectra of solid benzene under high pressure , 1985 .

[4]  W. Nellis,et al.  Equation of state and optical luminosity of benzene, polybutene, and polyethylene shocked to 210 GPa (2.1 Mbar) , 1984 .

[5]  P. W. Bridgman.  Freezings and Compressions to 50,000 kg/cm2 , 1941 .

[6]  P. W. Bridgman.  Freezing Parameters and Compressions of Twenty-One Substances to 50,000 Kg/Cm , 1942 .

[7]  M. Aubert-Frécon.  Spheroidal multipolar expansions for intermolecular energy in crystal theory. Lattice energy and cell dimensions of the orthorhombic structure of benzene crystal , 1979 .

[8]  E. Bernstein.  Calculation of Ground State Vibrational Structure and Phonons of the Isotopic Benzene Crystals , 1970 .

[9]  S. Block,et al.  Polymorphism in Benzene, Naphthalene, and Anthracene at High Pressure , 1970, Science.

[10]  Stanley Block,et al.  Calibration of the pressure dependence of the R1 ruby fluorescence line to 195 kbar , 1975 .

[11]  G. E. Leroi,et al.  Reassignment of Librational Symmetries in Benzene. , 1973 .

[12]  A. Dzyabchenko.  Theoretical structures for crystalline benzene. Part 5. Static equilibrium at negative pressures , 1986 .

[13]  J. D. Isdale,et al.  Transport properties of nonelectrolyte liquid mixtures—IV. Viscosity coefficients for benzene, perdeuterobenzene, hexafluorobenzene, and an equimolar mixture of benzene + hexafluorobenzene from 25 to 100°c at pressures up to the freezing pressure , 1981 .

[14]  E. R. Andrew,et al.  A nuclear magnetic resonance investigation of three solid benzenes , 1953, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[15]  A. Fruhling.  Low Frequency Raman Spectrum of a Benzene Single Crystal , 1950 .

[16]  A. Dzyabchenko,et al.  Theoretical structure of crystalline benzene. III. Hydrostatic pressure effect , 1986 .

[17]  J. R. Ruble,et al.  The crystal structure of deuterated benzene , 1987, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[18]  A. Lagendijk,et al.  Time‐resolved stimulated Raman scattering in a diamond anvil cell , 1987 .

[19]  S. Block,et al.  Crystallography of Some High‐Pressure Forms of C6H6, CS2, Br2, CCl4, and KNO3 , 1969 .

[20]  T. Shimanouchi,et al.  Normal Vibrations and Intermolecular Forces of Crystalline Benzene and Naphthalene , 1966 .

[21]  C. E. Weir,et al.  Crystal Structure of Benzene II at 25 Kilobars , 1969, Science.

[22]  T. Shimanouchi,et al.  Far‐Infrared Spectra of Crystalline Benzene at 138°K and Intermolecular Forces , 1967 .

[23]  H. Szwarc,et al.  Pressure and temperature shifts of librational modes in solid benzene: the isochores and the proportionality between the thermal expansion and isothermal compressibility tensors , 1975 .

[24]  E. Bright Wilson,et al.  The Normal Modes and Frequencies of Vibration of the Regular Plane Hexagon Model of the Benzene Molecule , 1934 .

[25]  W. F. Sherman.  Bond anharmonicities, Gruneisen parameters and pressure-induced frequency shifts , 1980 .

[26]  D. Dows,et al.  Absolute Infrared Intensities in Crystalline Benzene , 1962 .

[27]  Mitsuo. Ito.  Raman Spectrum of Benzene Crystal , 1965 .

[28]  A. Fuchs,et al.  Pressure-volume-temperature relations for crystalline benzene , 1978 .

[29]  J. T. Woo,et al.  Raman spectra and defect fluorescence of anthracene and naphthalene crystals at high pressures and low temperatures , 1975 .

[30]  T. Shigeoka,et al.  Raman spectra of benzene and benzene-d6 crystals , 1966 .

[31]  M. Nicol,et al.  Raman spectra of solid benzene under high pressures , 1974 .

[32]  G. W. Robinson,et al.  Raman Spectrum of Crystalline Benzene , 1967 .

[33]  J. Leger.  Volume of benzene under very high pressure , 1988 .

[34]  Thomas L. Starr,et al.  Calculation of the crystal structures of hydrocarbons by molecular packing analysis , 1977, Comput. Chem..

[35]  R. D. Dick.  Shock Wave Compression of Benzene, Carbon Disulfide, Carbon Tetrachloride, and Liquid Nitrogen , 1970 .

[36]  W. Kiefer,et al.  Raman studies of pressure‐induced frequency shifts in d0‐ and d8‐naphthalene , 1982 .

[37]  A. Ron,et al.  Far-infrared lattice vibrations of crystalline benzene , 1973 .

[38]  D. Ravot,et al.  Anomalous behavior of CeTe under high pressures , 1983 .

[39]  P. Wong,et al.  Raman spectroscopy under pressure using a diamond pressure vessel , 1974 .

[40]  R. Zallen.  Pressure-Raman effects and vibrational scaling laws in molecular crystals: S 8 and As 2 S 3 , 1974 .

[41]  H. Bonadeo,et al.  Infrared Spectra in Polarized Light of Crystalline Benzene and Benzene‐d6 , 1970 .

[42]  R. K. Crawford,et al.  Pressure dependence of the lattice frequencies of anthracene and naphthalene , 1973 .

[43]  S. Califano,et al.  Calculation of crystal vibrations of benzene , 1973 .

[44]  L. Salem,et al.  Forces in the benzene crystal , 1966 .

[45]  D. Cruickshank,et al.  The crystal structure of benzene at — 3°C , 1958, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[46]  K. Tohji,et al.  Direct Observation of Phase Transformation Process by Energy-Dispersive X-Ray Diffractometry , 1980 .

[47]  D. E. Williams,et al.  The effect of Coulombic interactions on the calculated crystal structures of benzene at atmospheric and 25 kbar pressure , 1975 .

[48]  G. Kennedy,et al.  Phase Diagram of Benzene to 35 kbar , 1971 .

[49]  H. Gebbie,et al.  Sub-millimetre Wave Spectra of Non-polar Liquids and Crystals , 1967, Nature.

[50]  G. E. Bacon,et al.  A crystallographic study of solid benzene by neutron diffraction , 1964, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[51]  E. Castellucci,et al.  Raman Spectrum of a Single Crystal of Benzene , 1972 .

[52]  A. Ron,et al.  Lattice vibrations of crystalline benzene. II—Librational modes , 1976 .

[53]  D. Hornig,et al.  The Vibrational Spectra of Molecules and Complex Ions in Crystals. II. Benzene , 1949 .

[54]  Taro Takahashi,et al.  X‐Ray Diffraction and Optical Observations on Crystalline Solids up to 300 kbar , 1967 .