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An extension of the CRYSTAL program is presented allowing for calculations of anharmonic infrared (IR) intensities and Raman activities for periodic systems. This work is a follow-up of two papers devoted to the computation of anharmonic vibrational states of solids from DFT (density functional theory) calculations (Erba et al. J. Chem. Theory Comput. 2019, 15, 3755-3765 and Erba et al. J. Chem. Theory Comput. 2019, 15, 3766-3777). The approach presented here relies on the evaluation of integrals of the dipole moment and polarizability operators over anharmonic wave functions obtained from either VSCF (vibrational self-consistent field) or VCI (vibrational configuration interaction) calculations. With this extension, the program now allows for a more complete characterization of the vibrational spectroscopic features of solids within the density functional theory. In particular, it is able (i) to provide reliable positions and intensities for the most intense spectral features and (ii) to check whether a first overtone or a combination band has a nonvanishing IR intensity or Raman activity. Therefore, it becomes possible to assign the transition(s) corresponding to satellite peak(s) around a fundamental transition or the overtones or combination bands that may be as intense as their corresponding fundamental transitions through the strongest mode-mode couplings, as in so-called Fermi resonances. The present method is assessed on two molecular systems, H 2 O and H 2 CO, as well as on two solid state cases, boron hydrides BH 4 and their deuterated species BD 4 in a crystalline environment of alkali metals (M = Na, K). The solid state cases are particularly insightful as, in the B-H (or B-D) stretching region here considered, they exhibit many spectral features entirely due to anharmonic effects: two out of three in the IR spectrum and four out of six in the Raman spectrum. All IR and Raman active overtones and combination bands experimentally observed are correctly predicted with our approach. The effect of the adopted quantum-chemical model (DFT exchange-correlation functional/basis set) for the electronic structure calculations on the computed spectra is discussed and found to be significant, which suggests some special care is needed for the analysis of subtle spectral features.

Calculation of Anharmonic IR and Raman Intensities for Periodic Systems from DFT Calculations: Implementation and Validation