School of Engineering, Swansea University, Singleton Park, Swansea SA2 8PP, United Kingdom.
J Chem Phys. 2009 Dec 7;131(21):214509. doi: 10.1063/1.3268702.
A rounded stretched exponential function is introduced, C(t)=exp{(tau(0)/tau(E))(beta)[1-(1+(t/tau(0))(2))(beta/2)]}, where t is time, and tau(0) and tau(E) are two relaxation times. This expression can be used to represent the relaxation function of many real dynamical processes, as at long times, t>>tau(0), the function converges to a stretched exponential with normalizing relaxation time, tau(E), yet its expansion is even or symmetric in time, which is a statistical mechanical requirement. This expression fits well the shear stress relaxation function for model soft soft-sphere fluids near coexistence, with tau(E)<<tau(0). The function gives the correct limits at low and high frequency in Cole-Cole plots for dielectric and shear stress relaxation (both the modulus and viscosity forms). It is shown that both the dielectric spectra and dynamic shear modulus imaginary parts approach the real axis with a slope equal to 0 at high frequency, whereas the dynamic viscosity has an infinite slope in the same limit. This indicates that inertial effects at high frequency are best discerned in the modulus rather than the viscosity Cole-Cole plot. As a consequence of the even expansion in time of the shear stress relaxation function, the value of the storage modulus derived from it at very high frequency exceeds that in the infinite frequency limit (i.e., G(infinity)).
引入了一种圆形拉伸指数函数,C(t)=exp{(tau(0)/tau(E))(beta)[1-(1+(t/tau(0))(2))(beta/2)]},其中 t 是时间,tau(0) 和 tau(E) 是两个弛豫时间。这个表达式可以用来表示许多真实动力学过程的弛豫函数,因为在长时间,t>>tau(0),函数收敛到具有归一化弛豫时间 tau(E)的拉伸指数,但它的展开在时间上是偶数或对称的,这是统计力学的要求。这个表达式很好地拟合了模型软球软流体在共存附近的剪切应力弛豫函数,其中 tau(E)<<tau(0)。该函数在介电和剪切应力弛豫(模量和粘度形式)的 Cole-Cole 图中在低频和高频处都有正确的限制。结果表明,介电谱和动态剪切模量虚部在高频下都以斜率等于 0 接近实轴,而在相同极限下动态粘度具有无限斜率。这表明在高频下,惯性效应在模量而不是粘度 Cole-Cole 图中更容易识别。由于剪切应力弛豫函数在时间上的偶数展开,从它导出的存储模量在非常高的频率下的值超过了无限频率极限(即 G(infinity))。