The lifetimes of quantum excitations are directly related to the electron and phonon energy linewidths of a particular scattering event. Using the versatile double time thermodynamic Green’s function approach based on many-body theory, an ab-initio formulation of relaxation times of various contributing processes has been investigated with newer understanding in terms of the linewidths of electrons and phonons. The energy linewidth is found to be an extremely sensitive quantity in the transport phenomena of crystalline solids as a collection of large number of scattering processes, namely, boundary scattering, impurity scattering, multiphonon scattering, interference scattering, electron–phonon processes and resonance scattering. The lattice thermal conductivities of three samples of GaAs have been analysed on the basis of modified Callaway model and a fairly good agreement between theory and experimental observations has been reported.