First-principles study of the high-pressure behavior of crystalline benzoic acid

Abstract

In this work, a detailed study of the structural, electronic and optical absorption properties of crystalline benzoic acid in the pressure range of 0–300[Formula: see text]GPa is performed by density functional theory (DFT) calculations. We found that occur complex transformations in benzoic acid under compression occurs, by analyzing the variation tendencies of the lattice constants, bond lengths and bond angles under different pressures. In the pressure range 0–280[Formula: see text]GPa, repeated formations and disconnections of hydrogen bonds between H1(P1) atom and O1(P1), O2(P4-[Formula: see text]-[Formula: see text]-[Formula: see text]) atoms occur several times, and a new eight-atom ring (benzoic acid dimer) forms at 100[Formula: see text]GPa and 280[Formula: see text]GPa. Then, by analyzing the band gap and density of states (DOS) of benzoic acid, it is found that the crystal undergoes a phase transformation from insulator to semiconductor at 240[Formula: see text]GPa and it even becomes metal phase at 280[Formula: see text]GPa. In addition, the relatively high optical activity with the pressure increases of benzoic acid is seen from the absorption spectra, and three obvious structural transformations are also observed at 110, 240 and 290[Formula: see text]GPa, respectively.