Composition dependent phase stability of Ni–Mn–Ga alloys studied by ab initio calculations

•Composition dependent phase stability was studied by ab initio calculations.•Ni-doping relatively stabilizes NM, whereas proper Mn-doping stabilizes 7M.•Martensitic transformation experiences much larger driving force.•Bonds between Ni and Mn is beneficial to the stability of the modulated martensite. Composition dependent phase stability of Ni–Mn–Ga magnetic shape memory alloys was studied by first-principles density-functional calculations. It is demonstrated that the three kinds of doping (Ni substitution for Mn, Ni for Ga, and Mn for Ga) destabilize all the three structures. However, Ni-doping relatively stabilizes the non-modulated martensite (NM) with simple tetragonal crystal structure, whereas proper Mn-doping relatively stabilizes the monoclinic seven-layered modulated (7M) martensite with monoclinic structure. Comparing the energy difference between the parent and the product phases, we found that martensitic transformation experiences much larger driving force than that of the intermartensitic transformation. Chemical bonds between Ni and Mn are observed not only with the stoichiometric Mn, but also with the excess ones. Bonds between Ni and Mn in modulated martensite is stronger than that of the non-modulated martensite, which is beneficial to the stability of the modulated martensite. The present result provides useful information for further development of magnetic shape memory alloys that is difficult to be obtained from experiments.