Definition Peculiarities of Energy of Vacancy Formation in 4d-Transition Metals from First Principles

Сергій Олександрович Замулко


In this paper a study of the temperature dependence of the vacancy formation energy in bulk fcc 4d-transition metals Ag and Pd using DFT was presented. Peculiarity of this work is the use of experimental values of the lattice parameters for the respective temperatures. This paper discusses the various contributions to the vacancy formation energy and shows that they can play an important role. It was shown that thermal excitation has a significant impact on the vacancy formation energy at high temperatures. The possibility of the existence of the compensation effect, i.e. the simultaneous changes in the contributions of the free energy and the vacancy formation energy in the fcc 4d-transition metals Ag and Pd, which were investigated from first principles. Taking in to account free oscillation energy and electronic thermal excitation depending on the temperature allows obtaining a qualitative picture of the effect of thermal expansion. The vacancy formation energy is in good agreement with previous theoretical and experimental studies. The effect of mutual compensation of different contributions to the vacancy formation energy can explain the constant value of the vacancy formation energy at any temperature and justifies the neglect of the temperature dependence of the simulation properties.


Density functional theory; The energy of formation of vacancies; The first principles; Electronic thermal exitation; Vibration energy


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