We have assessed the assumption of local thermodynamic equilibrium in a shock wave by comparing local thermodynamic data generated with nonequilibrium molecular dynamics (NEMD) simulations with results from corresponding equilibrium simulations. The shock had a Mach number approximately equal to 2 in a Lennard-Jones spline liquid. We found that the local equilibrium assumption holds perfectly well behind the wave front, and is a very good approximation in the front itself. This was supported by calculations of the excess entropy production in the shock front with four different methods that use the local equilibrium assumption in different ways. Two of the methods assume local equilibrium between excess thermodynamic variables by treating the shock as an interface in Gibbs's sense. The other two methods are based on the local equilibrium assumption in a continuous description of the shock front. We show for the shock studied in this work that all four methods give excess entropy productions that are in excellent agreement, with an average variance of 3.5% for the nonequilibrium molecular dynamics (NEMD) simulations. In addition, we solved the Navier-Stokes (N-S) equations numerically for the same shock wave using an equilibrium equation of state (EoS) based on a recently developed perturbation theory. The results for the density, pressure, and temperature profiles agree well with the profiles from the NEMD simulations. For instance, the shock waves generated in the two simulations travel with almost the same speed; the average absolute Mach-number deviation of the N-S simulations relative to NEMD is 2.6% in the investigated time interval.