On the Transformation of light into Heat in Solids. I

TLDR

Electronic excitation in a crystal is delocalized as excitation waves, analogous to sound waves, rather than being confined to individual atoms. The excitation state splits into n substates forming an excitation multiplet, and superposing excitation waves produces excitation packets that propagate between atoms, each substate corresponding to a slightly different crystal structure and vibrational state. The excitation-induced shift in vibrational states indirectly couples them, enabling excitation energy to be shared among hundreds of heat oscillators without direct coupling or anharmonicity during the radiationless transition that constitutes the second step of light absorption.

Abstract

Starting from the analogy between a crystal and molecule, it is shown that the electronic excitation, forming the first step in the process of light absorption, is not confined to a particular atom, but is diluted between all of them in the form of "excitation waves," similar to sound waves which are used to describe the heat motion in the same crystal. Owing to the interaction between the atoms the excitation state is split up into substates whose number is equal to the number of atoms $n$ (excitation multiplet). By superposing several excitation waves "excitation packets" can be constructed representing the travelling of the excitation state from one atom to another. To each excitation sub-state there corresponds a definite crystal structure (lattice constant, vibration frequencies) slightly different from that of the normal, and giving rise to slightly different vibrational states. This influence of the excitation on the vibrational states provides an indirect coupling between them, which allows the excitation energy to be shared between a few hundred heat-oscillators with practically no direct coupling nor anharmonicity in a radiationless transition which forms the second state of the process of light absorption.