Pressure-dependent structural and electronic properties of quasi-one-dimensional (TMTTF)2PF6

We have performed detailed x-ray investigations of the quasi-one-dimensional organic conductor (TMTTF)(2)PF(6) at room temperature and hydrostatic pressures up to 27 kbar. Based on the pressure-dependent crystal structure, the electronic band structure was calculated by density functional theory (DFT). Our systematic study provides important information on the coupling among the organic molecules but also to the anions. We discuss the consequences for the electronic properties and compare them with optical investigations under pressure. The increasing plasma frequency observed perpendicular to the stacks corresponds to a widening of the bands for the b-direction. Around 20 kbar a dimensional crossover occurs from a one-dimensional Mott insulator to a two-dimensional metal.