High-pressures study by Raman spectroscopy and DFT calculations of L-tyrosine hydrobromide crystal

Abstract The high-pressure Raman spectra of L-tyrosine hydrobromide crystal (LTHBr) were obtained from 1.0 atm to 8.1 GPa in the 100–3200 cm−1 spectral region. The structural conformation and dimensions of the monoclinic unit cell were estimated using the powder X-ray diffraction (PXRD) method and Rietveld refinement using the GSAS program. At atmospheric pressure, the Raman spectrum was obtained in the spectral range of 100–3200 cm−1 and the assignment of the normal modes based on density functional theory calculations was provided. Large wavenumber shifts of modes at 106, 123, and 157 were observed, which were interpreted as the large displacement of the atoms, making the molecule a flexible structure. The change in the slope (dɷ / dP) of these bands between the pressures of 3.0 and 4.0 GPa and the appearance of a mode of low wavenumber indicate the occurrence of a structural phase transition. A band initially observed at 181 cm−1 in the spectrum recorded at 0.7 GPa change the relative intensity with a band at 280 cm−1 (recorded at 5.8 GPa), indicating a conformational transition. In the region of the internal modes, the spectra show changes that reinforce the conformational phase transition since the bands initially at 1247 and 1264 cm−1 observed at 1.0 GPa have their intensities reversed, and at 3.0 GPa it is observed the fusion of the bands at 1264 and 1290 cm−1 (values recorded at ambient pressure). Thus, we can assume that the LTHBr crystal has undergone a structural phase transition and a conformational phase transition in the pressure range investigated.