Two‐Photon Absorption by Envelope–Hole Coupled Exciton States in Cubic ZnSe. I. Energy Spectrum of the Hd Term and Valence‐Band Parameters

In the exciton spectrum of cubic ZnSe a fourfold energy splitting of the 2P exciton is observed by two‐photon absorption. The distinct fine structure is the first experimental evidence for the coupling between the exciton envelope and the total hole spin. The energy spectrum of the spin Hamiltonian for Wannier excitons is calculated by use of a variational technique. Hydrogenic p‐ and f‐like trial functions are introduced as solutions, and the two equivalent Bohr radii are treated as independent variational parameters. First experimental data of the hole effective‐mass parameters for the Γ8 valence band are deduced from the observed energy splitting.