Elucidating the phase transitions of decanoic-acid crystal by XRD, Raman, group theory and Gibbs energy analyses combined with DFT calculations.

This research reports a series of phase transitions in the decanoic-acid (DA) crystal under low-temperature conditions, which were elucidated by XRD, Raman scattering and DFT calculations in a dimer of DA in the C form (monoclinic structure). The first phase change was noticed within the 210-190 K interval duly characterized as a transition of second-order type, as indicated by Gibbs energy behavior, suggesting that the monoclinic structure (P2/c) of the crystal is not changed. The second change was observed nearly 110-90 K, whose transition is first-order type occurring from the C form to an A form (triclinic), possibly belonging to the P1 space group. This new polymorphic phase was duly predicted through DFT calculations. According to Gibbs energy behavior, the third phase change (∼30-10 K) is proposed to be a transition from the A form to a new polymorphic phase that probably is a first-order transition, likely associated with a change from the P1 space group to P-1. Furthermore, group theory and wavenumber vs temperature plots' analyses corroborated the phase transitions undergone by DA crystal. In addition, anharmonicity effects in several Raman bands' behavior were noticed during the cooling. A correct assignment for the Raman and IR modes via DFT calculations at room-temperature conditions is also provided herein.