Excess entropy scaling of transport properties of Lennard-Jones chains

Abstract

Excess-entropy scaling relationships for diffusivity and viscosity of Lennard-Jones chain fluids are tested using molecular dynamics simulations for chain sizes that are sufficiently small that chain entanglement effects are insignificant. The thermodynamic excess entropy S(e) is estimated using self-associating fluid theory (SAFT). A structural measure of the entropy S(2) is also computed from the monomer-monomer pair correlation function, g(m)(r). The thermodynamic and structural estimators for the excess entropy are shown to be very strongly correlated. The dimensionless center-of-mass diffusivities, D(cm) (*), obtained by dividing the diffusivities by suitable macroscopic reduction parameters, are shown to conform to the excess entropy scaling relationship, D(cm) (*)=A(n) exp(alpha(n)S(e)), where the scaling parameters depend on the chain length n. The exponential parameter alpha(n) varies as -(1n) while A(n) varies approximately as n(-0.5). The scaled viscosities obey a similar relationship with scaling parameters B(n) and beta(n) where beta(n) varies as 1n and B(n) shows an approximate n(0.6) dependence. In accordance with the Stokes-Einstein law, for a given chain length, alpha(n)=-beta(n) within statistical error. The excess entropy scaling parameters associated with the transport properties therefore display a simple dependence on chain length.

Scaling of the dynamics of flexible Lennard-Jones chains

“…[36]. Moreover, the LJC liquid has been shown to obey Rosenfeld's excess entropy scaling [36,56,57,61].…”

“…Often, the neighboring segments in the chain are bonded by a FENE potential, although harmonic springs [40][41][42] and rigid bonds [36,56,57] have also been used. Here, the bond length l b = σ = 1 was kept constant using the Time Symmetrical Central Difference algorithm [58,59].…”

Modeling the viscosity of pure imidazolium-based ionic liquids using SAFT-VR-Mie EoS

“…The most popular ones are the free-volume theory (FVT) [7,8], the frictional theory (FT) and subsequent developments [9][10][11], the hard sphere scheme [12,13], extensions of the kinetic-theory to chains, [14,15] scaling relations with the residual entropy [16][17][18] and viscosity correlation such as Yarranton and Satyro method [19].…”

Water-like anomalies in the core-softened systems: Dependence on the trajectory in density-temperature plane

“…After that the excess entropy scaling was applied to many different systems including core-softened liquids [5,6,12,13,8], liquid metals [14,15], ionic liquids [16,17], network-forming liquids [12,16], water [18], chain fluids [19] and bounded potentials [8,20,21].…”