Influence of spin fluctuations on structural phase transitions of iron

Abstract

The effect of spin fluctuations on the $\ensuremath{\alpha}$ (bcc)-$\ensuremath{\gamma}$ (fcc)-$\ensuremath{\delta}$ (bcc) structural phase transitions in iron is investigated with a tight-binding (TB) model. The orthogonal $d$-valent TB model is combined with thermodynamic integration, spin-space averaging, and Hamiltonian Monte Carlo to compute the temperature-dependent free-energy difference between bcc and fcc iron. We demonstrate that the TB model captures experimentally observed phonon spectra of bcc iron at elevated temperatures. Our calculations show that spin fluctuations are crucial for both the $\ensuremath{\alpha}\text{\ensuremath{-}}\ensuremath{\gamma}$ and $\ensuremath{\gamma}\text{\ensuremath{-}}\ensuremath{\delta}$ phase transitions but they enter through different mechanisms. Spin fluctuations impact the $\ensuremath{\alpha}\text{\ensuremath{-}}\ensuremath{\gamma}$ phase transition mainly via the magnetic/electronic free-energy difference between bcc and fcc iron. The $\ensuremath{\gamma}\text{\ensuremath{-}}\ensuremath{\delta}$ phase transition, in contrast, is influenced by spin fluctuations only indirectly via the spin-lattice coupling. Combining the two mechanisms, we obtain both the $\ensuremath{\alpha}\text{\ensuremath{-}}\ensuremath{\gamma}$ and $\ensuremath{\gamma}\text{\ensuremath{-}}\ensuremath{\delta}$ phase transitions with our TB model. The calculated transition temperatures are in very good agreement with experimental values.