Journal of Physical Chemistry B, Vol.120, No.28, 7003-7015, 2016
Critical Slowing of Density Fluctuations Approaching the Isotropic-Nematic Transition in Liquid Crystals: 2D IR Measurements and Mode Coupling Theory
Two-dimensional infrared (2D IR) data are presented for a vibrational probe in three nematogens: 4-cyano-4'-pentylbiphenyl, 4-cyano-4'-octylbiphenyl, and 4-(trans-4-amylcyclohexyl)-benzonitrile. The spectral diffusion time constants in all three liquids in the isotropic phase are proportional to [T*/(T - T*)](1/2), where T* is 0.5-1 K below the isotropic nematic phase transition temperature (T-NI). Rescaling to a reduced temperature shows that the decays of the frequency frequency correlation function (FFCF) for all three nematogens fall on the same curve, suggesting a universal dynamic behavior of nematogens above T-NI. Spectral diffusion is complete before significant orientational relaxation in the liquid, as measured by optically heterodyne detected-optical Kerr effect (OHD-OKE) spectroscopy, and before any significant orientational randomization of the probe measured by polarization selective IR pump-probe experiments. To interpret the OHD-OKE and FFCF data, we constructed a mode coupling theory (MCT) schematic model for the relationships among three correlation functions: phi(1), a correlator for large wave vector density fluctuations; phi(2), the orientational correlation function whose time derivative is the observable in the OHD-OKE experiment; and phi(3), the FFCF for the 2D IR experiment. The equations for phi(1) and phi(2) match those in the previous MCT schematic model for nematogens, and phi(3) is coupled to the first two correlators in a straightforward manner. Resulting models fit the data very well. Across liquid crystals, the temperature dependences of the coupling constants show consistent, nonmonotonic behavior. A remarkable change in coupling occurs at similar to 5 K above T-NI, precisely where the rate of spectral diffusion in 5CB was observed to deviate from that of a similar nonmesogenic liquid.