Jose, Prasanth P and Bagchi, Biman (2004) In search of temporal power laws in the orientational relaxation near isotropic–nematic phase transition in model nematogens. In: Journal of Chemical Physics, 120 (23). pp. 11256-11266.
Recent Kerr relaxation experiments by Gottke et al. [J. Chem. Phys. 116, 360 (2002); 116, 6339 (2002)] have revealed the existence of a pronounced temporal power law decay in the orientational relaxation near the isotropic–nematic phase transition (INPT) of nematogens of rather small aspect ratio, k(k=3–4). We have carried out very long (50 ns) molecular dynamics simulations of model (Gay–Berne) prolate ellipsoids with aspect ratio 3 in order to investigate the origin of this power law. The model chosen is known to undergo an isotropic to nematic phase transition for a range of density and temperature. The distance dependence of the calculated angular pair correlation function correctly shows the emergence of a long range correlation as the INPT is approached along the density axis. In the vicinity of INPT, the single particle second rank orientational time correlation function exhibits power law decay, (t–alpha) with exponent alpha~2/3. More importantly, we find the sudden appearance of a pronounced power-law decay in the collective part of the second rank orientational time correlation function at short times when the density is very close to the transition density. The power law has an exponent close to unity, that is, the correlation function decays almost linearly with time. At long times, the decay is exponential-like, as predicted by Landau–de Gennes mean field theory. Since Kerr relaxation experiments measure the time derivative of the collective second rank orientational pair correlation function, the simulations recover the near independence of the signal on time observed in experiments. In order to capture the microscopic essence of the dynamics of pseudonematic domains inside the isotropic phase, we introduce and calculate a dynamic orientational pair correlation function (DOPCF) obtained from the coefficients in the expansion of the distinct part of orientational van Hove time correlation function in terms of spherical harmonics. The DOPCF exhibits power law relaxation when the pair separation length is below certain critical length. The orientational relaxation of a local director, defined in terms of the sum of unit vectors of all the ellipsoidal molecules, is also found to show slow power law relaxation over a long time scale. These results have been interpreted in terms of a newly developed mode coupling theory of orientational dynamics near the INPT. In the present case, the difference between the single particle and the collective orientational relaxation is huge which can be explained by the frequency dependence of the memory kernel, calculated from the mode coupling theory. The relationship of this power law with the one observed in a supercooled liquid near its glass transition temperature is explored.
|Item Type:||Journal Article|
|Additional Information:||Copyright for this article belongs to American Institute of Physics (AIP)|
|Department/Centre:||Division of Chemical Sciences > Solid State & Structural Chemistry Unit|
|Date Deposited:||16 Aug 2004|
|Last Modified:||19 Sep 2010 04:14|
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