Effective method for the computation of optical spectra of large molecules at finite temperature including the Duschinsky and Herzberg-Teller effect: The Qx band of porphyrin as a case study.

The authors extend their recent method for the computation of vibrationally resolved optical spectra of large molecules, including both the Duschinsky rotation and the effect of finite temperature in the framework of the Franck-Condon (FC) approximation, to deal with the more general case of the Herzberg-Teller (HT) model, where also the linear dependence of the transition dipole moment on the nuclear coordinates is taken into account. This generalization allows us to investigate weak and vibronically allowed transitions by far extending the range of application of the method. The calculation of the spectra of sizable molecules is computationally demanding because of the huge number of final vibrational states that must be taken into account, and the inclusion of HT terms further increases the computational burden. The method presented here automatically selects the relevant vibronic contributions to the spectrum, independent of their frequency, and it is able to provide fully converged spectra with a modest computational requirement. The effectiveness of the method is illustrated by computing the HT absorption and fluorescence Q(x) spectra of free-base porphyrin both at T=0 K and at room temperature, performing for the first time an exact treatment of vibrations in harmonic approximation. Q(x) spectra are compared to experiments and FC/HT interferences are analyzed in detail.