We propose two new thermostats which can be employed in computer simulations to ensure that two different variants of the configurational temperature fluctuate around their equilibrium values. These new thermostats differ from one previously introduced by Delhommelle and Evans [Mol. Phys. 99, 1825 (2001)] in several important ways. First, our thermostats are derived in the same spirit as the Nosé-Hoover thermostat and therefore generate the canonical phase-space distribution. Second, our thermostats involve simpler equations of motion, which do not involve spatial gradients of the configurational temperature. They do not suffer from problems stemming from stiff equations of motion and furthermore, in large temperature perturbation simulations, the measured temperature follows the set-point temperature without any overshoot, and with good damping of oscillations. We show that both of our configurational thermostats are special cases of a more general set of Nosé-Hoover equations proposed by Kusnezov et al. [Ann. Phys. 204, 155 (1990)]. The new thermostats are expected to be highly useful in nonequilibrium simulations, particularly those characterized by spatial inhomogeneities. They should also find applicability in simulations involving large changes in temperature over small time scales, such as temperature quench molecular dynamics and radiation damage modeling.

In this work we use nonequilibrium molecular dynamics (NEMD) to simulate an atomic liquid undergoing gravity-fed flow down a narrow channel. We compare the simulation results against the predictions of classical Navier-Stokes theory for two different channel widths. For a channel width of 5.1 molecular diameters, we find that the velocity profile deviates significantly from the hydrodynamic prediction. The shape of this velocity profile is found to be independent of the applied field (pressure gradient). We find that the heat flux profile does not agree with the cubic profile predicted by Navier-Stokes hydrodynamics, but shows significant oscillations located about one molecular diameter from the walls. This result differs from the earlier work of Todd and Evans [B. D. Todd and D. J. Evans, J. Chem. Phys. 103, 9804 (1995)], in which an assumption of a purely quadratic velocity profile resulted in very weak oscillations in the heat flux. We find that in narrow channels the viscosity cannot be described by a linear, local constitutive relation. However, classical Navier-Stokes behavior is approached for a channel width of >∼10 molecular diameters.

We present results from nonequilibrium molecular dynamics (NEMD) simulations of simple fluids undergoing planar Poiseuille flow in a slit pore only a few molecular diameters in width. The calculations reported in this publication build on previous results by including the effects of attractive forces and studying the flow at narrower pore widths. Our aims are: (1) to examine the role of attractive forces in determining hydrodynamic properties, (2) to provide clearer evidence for the existence of a non-Markovian generalization of Newtons law, (3) to examine the slip-stick boundary conditions in more detail by using a high spatial resolution of the streaming velocity profiles, (4) to investigate the significance of the recently proposed cross-coupling coefficient on the temperature profiles. The presence of attractive interactions gives rise to interesting packing effects, but otherwise, does not significantly alter the spatial dependence of hydrodynamic quantities. We find the strongest evidence to date that Newton’s Law breaks down for very narrow pores; the shear viscosity exhibits singularities. We suggest a method to test the validity of the non-Markovian generalization of Newton’s Law. No-slip boundary conditions are found to apply, even at these microscopic length scales, provided one takes into account the finite size of the wall atoms. The effects of any strain rate induced coupling to the heat flow are found to be insignificant.

In this article we show that atomic thermostats which have been used in the past for nonequilibrium molecular dynamics (NEMD) simulations of molecular fluids were incorrectly formulated. The error stems from an incorrect assumption made about the form of the streaming angular velocity. This assumption is incorrect even in the linear regime. One spurious effect of this atomic thermostat is the generation of a nonsymmetric pressure tensor. We outline a general method, based on a variational principle, for calculating the position and orientation dependent streaming velocity. Using this streaming velocity we develop an atomic thermostat for molecular fluids which does not bias the positional or orientational distribution functions for the fluid. The new atomic thermostat is validated in NEMD simulations of liquid chlorine undergoing planar Couette flow.

Results from extensive nonequilibrium molecular dynamics (NEMD) simulations are presented for liquid chlorine subject to planar Couette flow. Comparisons are made between the so-called atomic and molecular SLLOD algorithms [R. Edberg, G. P. Morriss, and D. J. Evans, J. Chem. Phys. 86, 4555 (1987)] with atomic and molecular thermostats, respectively. These two thermostats differ in the assumptions that are made regarding the streaming velocity. Both thermostats are responsible for the production of string phases characterized by a translational ordering at very high strain rates. In addition, the atomic thermostat is responsible for the existence of a nonvanishing antisymmetric stress and enhanced orientational ordering.