Affiliation:
1. Université de Lorraine–Nancy, CNRS, LEMTA Nancy France
2. Sorbonne Université, CNRS‐INSU, Institut des Sciences de la Terre, ISTeP UMR 7193 Paris France
3. Université de Lorraine–Nancy, CNRS, LPCT, UMR 7019 Nancy France
4. Accademia Delle Science di Torino Torino Italy
Abstract
AbstractThe KScF perovskite has been used as a model for investigating the relative importance of the Jahn‐Teller (JT) lift of degeneracy, the ScF octahedra rotation (OR), and the quadrupole‐quadrupole interaction linked to different occupancy of the Sc t subshell in various sites of the unit cell (orbital ordering, OO). The group‐subgroup sequence , , , and , supplemented by and , has been explored by using an Gaussian type basis set, hybrid functionals, and the CRYSTAL17 code. The JT lift of degeneracy provides a stabilization about 5 times larger than the sum of the OO and OR effects. The energy gained in the transition from to , consisting in a rotation of the octahedra around the axis, is 1077 E. From to , additional rotations around the and axes are possible, and the Sc electron can occupy a different t orbital, with a total energy reduction of 2318 E. The rotation of the octahedra reduces the strength of superexchange: in going from to the G‐AFM stabilization with respect to FM shrinks by a factor 4.
Subject
Computational Mathematics,General Chemistry