Anharmonic effects in the low-frequency vibrational modes of aspirin and paracetamol crystals

The low-frequency range of vibrational spectra is sensitive to collective vibrations of the lattice. In molecular crystals, it can be decisive in identifying the structure of different polymorphs and, in addition, it plays an important role in the magnitude of the temperature-dependent component of vibrational free-energy differences between these crystals. We study the vibrational Raman spectra and vibrational density of states of different polymorphs of the flexible aspirin and paracetamol crystals based on dispersion-corrected density functional theory, density functional perturbation theory, and ab initio molecular dynamics. We examine the effect of quasiharmonic lattice expansion and compare the results of harmonic theory and the time-correlation formalism for vibrational spectra. Lattice expansion strongly affects the collective vibrations below 300 cm(-1), but it is significantly less important at higher frequencies, while thermal nuclear motion can be important in the full vibrational range. We also observe that the inclusion or neglect of many-body van der Waals dispersion interactions does not cause large differences in the low-frequency range of Raman spectra or vibrational density of states, provided the lattice constants are fixed. We obtain quantitative agreement with experimental room-temperature Raman spectra below 300 cm(-1) for all polymorphs studied. Examining the two-dimensional correlations between different vibrations, we find which modes show a larger degree of an harmonic coupling to others, providing a possible route to assess the accuracy of harmonic free-energy evaluations in different cases.