Assignment of terahertz vibrational modes of L-glutamine using density functional theory within generalized-gradient approximation

The crystal structure of L-glutamine is stabilized by a three-dimensional network of intermolecular hydrogen bonds.We utilize plane-wave density functional theory lattice-dynamics calculations within the generalized-gradient approximation（GGA）, Perdew–Burke–Ernzerhof（PBE）, PBE for solids（PBEsol）, PBE with Wu–Cohen exchange（WC）, and dispersion-corrected PBE, to investigate the effect of these intermolecular contacts on the absorption spectra of glutamine in the terahertz frequency range. Among these calculations, the solid-state simulated results obtained using the WC method exhibit a good agreement with the measured absorption spectra, and the absorption features are assigned with the help of WC. This indicates that the vibrational modes of glutamine were related to the combination of intramolecular and intermolecular motions, the intramolecular modes were dominated by rocking or torsion involving functional groups; the intermolecular modes mainly result from the translational motions of individual molecules, and the rocking of the hydrogenbonded functional groups.