Orbital dimerization-induced first-order structural phase transition: a case study in La3Ni2O7

First-order structural phase transition is a common phenomenon in materials that qualitatively alters their physical properties. Yet, the abrupt first-order nature is usually unexplained by realistic computations, implying an omission of important physics in describing the electronic structure of the nearby stable phases. Using the recently discovered nickelate superconductors La3Ni2O7 as a prototypical example, we demonstrate that such first-order nature is typically beyond intra-atomic correlation considered in state-of-the-art material computations. Instead, a full many-body treatment of low-energy active orbitals reveals a generic inter-atomic "orbital dimerization" mechanism of first-order structural phase transition, corresponding to abrupt energy reduction upon a spin-singlet bond formation. Such an inter-atomic correlation qualitatively changes not only the essential lattice bonding but also the characteristics of low-energy electronic properties across the transition, including transport, magnetism, and superconductivity. This strong mechanism and the developed computational framework are generally applicable to a wide variety of ionic materials, to produce valuable insights on atomic and electronic structures essential for their physical properties and functionalities.