Theory of optical spectra of impurity centres in crystals: general consideration of quadratic vibronic coupling

A method is proposed for the calculation of the spectra of the multiphonon transitions caused by the quadratic vibronic coupling with a phonon continuum. In the method, the time evolution of the final state is described by the path integrals. By applying the Stratonovich–Hubbard identity, the quadratic coupling is presented as the fluctuating linear coupling; the latter is calculated by the Lax method. As a result, the problem is reduced to the calculation of the determinants of matrices, the elements of which are given by the pair correlation functions of the contributing configurational coordinates. The method has been verified for the case of two mixed modes. Numerical calculations have also been made for a modified Debye model.