d-Orbital splitting in transition-metal complexes is central to magnetism, spectroscopy, and catalysis, yet its physical origin remains partly phenomenological in current models. This work introduces a structural reinterpretation in which orbital configurations arise as coherence-stable interference patterns, with ligand geometry acting as a boundary condition that selects allowed states. The result is a framework that preserves established results while suggesting new, testable deviations from standard ligand field behavior. This preprint presents a coherence-based extension of ligand field theory, in which orbital splitting is interpreted not solely as an electrostatic perturbation of predefined orbitals, but as a selection process among possible resonance configurations of the electron. A first phenomenological model is introduced that augments conventional crystal field contributions with a coherence-dependent stability term. This naturally allows for asymmetries, non-linear responses to distortion, and shifts in orbital ordering that are difficult to capture within purely electrostatic frameworks. The work outlines experimentally accessible predictions, including distortion-dependent orbital reordering, spin-state transitions, and spectroscopic signatures. These predictions are formulated in relative terms, enabling immediate comparison with existing experimental data. Rather than replacing established methods such as ligand field theory or density functional theory, the framework is intended as a complementary structural layer that may help reduce reliance on empirical parameterization and improve predictive consistency across related systems. If validated experimentally, this approach may contribute to a more unified understanding of orbital structure and support more systematically design-driven strategies in transition-metal chemistry, catalysis, and materials science.
Henrik Nilsson (Thu,) studied this question.