AbstractThe atomic site occupancy of alloying elements in the ZrCo2 and HfCo2 based Laves phases formed in the Co-9Al-9W-2Zr and Co-9Al-9W-2Hf alloys was experimentally determined by the combined techniques of energy-dispersive X-ray spectroscopy mapping with atomic resolution and the atom location by channeling enhanced microanalysis (ALCHEMI) method. The results show that both Al and W occupy the Zr site in the C15 and the Hf site in the C36 crystal structure. The atomic locations of Al and W were further confirmed by comparing calculated inelastic cross-sections with experimental ALCHEMI results. Using the determined atomic site occupancies of alloying elements, special quasirandom structure solid solution models with 192 atoms were constructed and employed in first-principles calculations. It is found theoretically that the energy of formation of the C15 structure is always lower than that of the C36 structure at 0 K in both ZrCo2 and HfCo2 phases, no matter whether Al and W are incorporated or not. However, further ab initio molecular dynamics simulations suggest that lattice vibration at finite temperature contributes significantly to the phase stability, stabilizing the C36 structure compared to the C15 type for the (Hf, Al, W)Co2 phase at finite temperature, which fits well with the experimental findings.