The interfacial structure in epitaxial Mo/W(001) superlattices, grown by magnetron sputtering on MgO(001) substrates has been studied. The films were grown in Ar and Kr discharges at a substrate temperature of 700 degrees C, and the as-deposited samples were analyzed by x-ray diffraction and found to be epitaxial with no high-angle grain boundaries. The degree of interfacial intermixing, caused by fluxes of different energetic species impinging on the growth surface, was estimated using a combination of Monte Carlo binary collision computer codes and a gas scattering computational model. In the Ar discharge case, large asymmetries in the Mo/W and W/Mo interfaces were found, with the W/Mo interface being more than a factor of 2 broader than the Mo/W interface. Simulations of x-ray reflectivity curves using the calculated interface profiles as input parameters without any additional fitting parameters agreed very well with measured data. The overall good fit between the calculated and measured reflectivity curves using the calculated compositional profiles is an indicator that the growth simulations using TRIM based codes provides interface profiles that are reasonably accurate, which can be used as a starting point for further refinements of the details of the interface structures.