The structural, thermochemical, and thermophysical properties of the AnCl₄, and NaCl-AnCl₄ (An = Th, U) melts were investigated using molecular dynamics (MD) simulations based on the Polarisable Ion Model (PIM). New force fields were proposed and used to compute key properties including density, thermal expansion, enthalpy of mixing, heat capacity, as well as the local structure and chemical speciation in the molten (Na, An)Cl_x (An = Th, U) salts. Thermodynamic models were then developed based on the CALPHAD method, using both PIM-MD and experimental data as input. Employing the modified quasichemical formalism in the quadruplet approximation for the liquid solution, the models account for the chemical speciation in the melt as calculated by MD simulations, and reproduce well phase equilibria in those systems. In particular, the models included monomeric and dimeric species to represent the physical nature of the ionic melt, which shows progressive oligomerisation with increasing AnCl₄ fraction. Our studies confirm that the melt becomes highly volatile at high AnCl₄ fractions, which is discussed in light of the results obtained herein.