Thermal conductivity heat flow may not be exactly the same as the direction of the thermal gradient. In metals, thermal conductivity approximately tracks electrical conductivity according to the Wiedemann–Franz law, as freely moving valence electrons transfer not only electric current but also heat energy. However, the general correlation between electrical and thermal conductance does not hold for other materials, due to the increased importance of phonon carriers for heat in non-metals. Highly electrically conductive silver is less thermally conductive than diamond, which is an electrical insulator, but due to its orderly array of atoms it is conductive of heat via phonons. The
Thermal conductivity because exact treatment as in the harmonic case is not possible and phonons are no longer exact eigensolutions to the equations of motion. Even if the state of motion of the crystal could be described with a plane wave at a particular time, its accuracy would deteriorate progressively with time. Time development would have to be described by introducing a spectrum of other phonons, which is known as the phonon decay. The two most important anharmonic effects are the thermal expansion and the phonon thermal conductivity. Only when the phonon number ‹n› deviates from the equilibrium value ‹n›, can a