Site-specific spin crossover in Fe₂TiO₄ post-spinel under high pressures to near a megabar

X-ray diffraction studies to ~90 GPa at room temperature show that Fe$_{2}$TiO$_{4}$ ferrous inverse spinel undergoes the following sequence of structural transitions : cubic (Fd3m) to tetragonal (I41/amd)to orthorhombic(Cmcm) to orthorhombic(Pmma),at the indicated onset transition pressures. Within the Cmcm phase, site-specific spin crossover is initiated and involves only highly distorted octahedral sites constituting ~25% of all Fe locations. This is manifest as a steeper volume decrease of dV/V0 ~ 3.5% beyond ~40 GPa and an emergent diamagnetic component discerned in 57Fe M\"ossbauer spectroscopy at variable cryogenic temperatures. A subsequent Cmcm to Pmma Fe/Ti disorder-order reconfiguration is facilitated at 6-fold coordinated (octahedral) sites. The rest of the high-spin Fe in 6-fold and 8-fold coordinated sites (~75% abundance) in the Pmma phase exhibit average saturation internal magnetic fields of H$_{hf}$ ~ 42 T to ~90 GPa, typical of spin-only (orbitally quenched) Fermi-contact values. By contrast average H$_{hf}$ ~ 20 T values, signifying unquenched orbital moments, occur below the 40-45 GPa spin-crossover initiation regime in the Cmcm phase. Therefore site-specific spin crossover invokes a cooperative lattice response and polyhedral distortions at the rest of the high-spin Fe sites, translating to 3d level (sub-band) changes and consequential orbital moment quenching. Near ~90 GPa Fe$_{2}$TiO$_{4}$ is a partially spin-converted chemically ordered Pmma post-spinel structure having a persistent charge gap of ~100 meV. Despite structural symmetry changes, partial spin crossover and lattice compressibility resulting in a ~33% total reduction in unit-cell volume and corresponding 3d bandwidth broadening, strong electron correlations persist at high densification.