Structural and orientational relaxation in supercooled liquid triphenylphosphite

Structural and orientational relaxation processes in the glass‐forming liquid triphenylphosphite (TPP) were studied by impulsive stimulated scattering, a time‐resolved four‐wave mixing technique. The α structural relaxation processes which can couple to the longitudinal and shear acoustic modes are analyzed phenomenologically in terms of a distribution of relaxation times fL(τL,T) or fS(τS,T), respectively, in the temperature range of 270–240 K. The two distributions appear to be identical, and undergo marked broadening as the sample is cooled. They are best described by a stretched exponential relaxation function whose exponent decreases with temperature. The molecular orientational relaxation times τor follow an Arrhenius temperature dependence and are longer than the average relaxation times 〈τL〉 and 〈τS〉 at high temperature, but converge as the temperature is lowered. We conclude that the observed orientational relaxation is decoupled from the α structural relaxation process and is a manifestation of ...

[1]  M. C. Lee,et al.  Depolarized stimulated gain spectra of liquid CS2 and benzene at room temperature , 1991 .

[2]  W. Grubbs,et al.  cw stimulated Brillouin gain spectroscopy of liquids , 1991 .

[3]  Keith A. Nelson,et al.  Femtosecond time-resolved spectroscopy of polarization dynamics in KNbO3 , 1991 .

[4]  K. Nelson,et al.  Picosecond–microsecond structural relaxation dynamics in polypropylene glycol: Impulsive stimulated light‐scattering experiments , 1991 .

[5]  K. Schmidt-Rohr,et al.  Nature of nonexponential loss of correlation above the glass transition investigated by multidimensional NMR. , 1991, Physical review letters.

[6]  S. Rice,et al.  An interpretation of the bifurcation of orientational relaxation processes in a supercooled liquid , 1990 .

[7]  S. M. Silence,et al.  Impulsive stimulated scattering study of normal and supercooled liquid triphenylphosphite , 1990 .

[8]  A. Polimeno,et al.  A many-body stochastic approach to rotational motions in liquids : complex decay times in highly viscous fluids , 1990 .

[9]  K. Nelson,et al.  Improved sample cell design for optical studies of glass-forming liquids in the 0-530 K range , 1990 .

[10]  W. Gotze The scaling functions for the β-relaxation process of supercooled liquids and glasses , 1990 .

[11]  Wu,et al.  Scaling in the relaxation of supercooled liquids. , 1990, Physical review letters.

[12]  E. Rössler,et al.  β-process of supercooled o-terphenyl: a comparison of dielectrical and NMR data guided by mode-coupling theory , 1990 .

[13]  S. Kivelson,et al.  Erratum: Models of rotational relaxation above the glass transition [J. Chem. Phys. 90, 4464 (1989)] , 1990 .

[14]  K. Nelson,et al.  Ultrasonic and hypersonic properties of molten KNO3–Ca(NO3)2 mixture , 1989 .

[15]  J. Etchepare,et al.  Polarization effects in femtosecond time-resolved coherent scattering from molecules in liquids , 1989 .

[16]  S. Greenfield,et al.  Anisotropic reorientational relaxation of biphenyl: Transient grating optical Kerr effect measurements , 1989 .

[17]  K. Nelson,et al.  The temperature‐dependent distribution of relaxation times in glycerol: Time‐domain light scattering study of acoustic and Mountain‐mode behavior in the 20 MHz–3 GHz frequency range , 1988 .

[18]  K. Nelson,et al.  Impulsive stimulated light scattering. I. General theory , 1987 .

[19]  K. Nelson,et al.  Intramolecular and intermolecular dynamics in molecular liquids through femtosecond time-resolved impulsive stimulated scattering , 1987 .

[20]  Jeong Frequency-dependent shear modulus of glycerol near the glass transition. , 1987, Physical review. A, General physics.

[21]  Bhattacharya,et al.  Ultrasonic investigation of the glass transition in glycerol. , 1986, Physical review. A, General physics.

[22]  Ramaswamy,et al.  Hydrodynamic theory of the glass transition. , 1985, Physical review letters.

[23]  D. Kivelson,et al.  A comprehensive light scattering study of a liquid composed of symmetric top molecules , 1982 .

[24]  Keith A. Nelson,et al.  Optical generation of tunable ultrasonic waves , 1982 .

[25]  K. Nelson,et al.  Laser-induced phonon spectroscopy. Optical generation of ultrasonic waves and investigation of electronic excited-state interactions in solids , 1981 .

[26]  R. Alfano,et al.  Relaxation kinetics of salol in the supercooled liquid state investigated with the optical Kerr effect , 1977 .

[27]  G. P. Johari,et al.  GLASS TRANSITION AND SECONDARY RELAXATIONS IN MOLECULAR LIQUIDS AND CRYSTALS , 1976 .

[28]  D. Kivelson,et al.  VH light scattering from triphenyl phosphite: Coupling of shear modes to molecular rotation , 1975 .

[29]  S. Dev,et al.  Further considerations of non symmetrical dielectric relaxation behaviour arising from a simple empirical decay function , 1971 .

[30]  H. G. Jerrard,et al.  Theories of Birefringence Induced in Liquids by Ultrasonic Waves , 1962 .

[31]  T. Litovitz,et al.  Ultrasonic Shear and Compressional Relaxation in Liquid Glycerol , 1957 .