Quantum Corrections to the Semiclassical Temperature Scale in the Structured Emission of Tetrahedral Complexes

Tetrahedral complexes with an excited state consisting of two closely lying triplet states are considered together with the full interaction hamiltonian, including ligand field, Jahn-Teller, pseudo Jahn-Teller, and spin-orbit interactions. The emission band shape is numerically calculated using Monte Carlo integration. The numerical calculations are applied to the PbWO4 system. Previous results using a semiclassical distribution function gave reasonable line shapes, but a mismatch with physical temperature. Using the correct quantum distribution function full correspondence with physical temperature is achieved.