64,277 research outputs found
Quantum diffusion in liquid para-hydrogen from ring-polymer molecular dynamics
We have used the ring-polymer molecular dynamics method to calculate approximate Kubo-transformed velocity autocorrelation functions and self-diffusion coefficients for low-pressure liquid para-hydrogen at temperatures of 25 and 14 K. The resulting diffusion coefficients are shown to be consistent with experimental shear viscosities and the established finite-size relation D(L)~=D([infinity])–2.837kBT/6pietaL, where kB is the Boltzmann constant, T the absolute temperature, eta the shear viscosity, and L the length of the (cubic) simulation cell. The diffusion coefficients D(L) obtained in simulations with finite system sizes are therefore too small. However, the extrapolation to infinite system size corrects this deficiency and leads to excellent agreement with experimental results. This both demonstrates the influence of system-size effects on quantum mechanical diffusion coefficients and provides further evidence that ring-polymer molecular dynamics is an accurate as well as practical way of including quantum effects in condensed phase molecular dynamics
Rheology of Ring Polymer Melts: From Linear Contaminants to Ring/Linear Blends
Ring polymers remain a major challenge to our current understanding of
polymer dynamics. Experimental results are difficult to interpret because of
the uncertainty in the purity and dispersity of the sample. Using both
equilibrium and non-equilibrium molecular dynamics simulations we have
systematically investigated the structure, dynamics and rheology of perfectly
controlled ring/linear polymer blends with chains of such length and
flexibility that the number of entanglements is up to about 14 per chain, which
is comparable to experimental systems examined in the literature. The smallest
concentration at which linear contaminants increase the zero-shear viscosity of
a ring polymer melt of these chain lengths by 10% is approximately one-fifth of
their overlap concentration. When the two architectures are present in equal
amounts the viscosity of the blend is approximately twice as large as that of
the pure linear melt. At this concentration the diffusion coefficient of the
rings is found to decrease dramatically, while the static and dynamic
properties of the linear polymers are mostly unaffected. Our results are
supported by a primitive path analysis.Comment: 5 pages, 4 figures, accepted by PR
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