Corrections of Electron–Phonon Coupling for Second-Order Structural Phase Transitions

Structural phase transitions are accompanied by a movement of one nucleus (or a few) in the crystallographic unit cell. If the nucleus movement is continuous, a second-order phase transition without latent heat results, whereas an abrupt nucleus displacement indicates a first-order phase transition with accompanying latent heat. Herein, a Hamiltonian including electron–phonon coupling (EPC) as proposed by Kristoffel and Konsel is taken. Contrary to their treatment, both the kinetic energy of the nucleus and its position are treated. The interaction of the many-electron system with the single nucleus is taken into account by the Born–Oppenheimer approximation and perturbative expressions for the free energies are derived. The nuclei corrections due to the entangled electrons are found to be minor, but highlight the importance of the symmetry breaking at low temperature. Furthermore the free energy for a canonical ensemble is computed, whereas Kristoffel and Konsel use a grand canonical ensemble, which allows to derive more stringent bounds on the free energy. For the zero-order nucleus correction, the shift of the phase transition temperature by evaluating the free energy is deduced.