title: Triggering dynamics of the high-pressure benzene amorphization.
abstract: Success in designing and tailoring solid-state reactions depends on the knowledge of the mechanisms regulating the reactivity at the microscopic level. In spite of several attempts to rationalize the reactivity of crystals, the question of the existence of a critical distance for a reaction to occur remains unsolved. In this framework, the role of lattice phonons, which continuously tune the relative distance and orientation of the molecules, is still not fully understood. Here, we show that at the onset of the transformation of crystalline benzene to an amorphous hydrogenated carbon the intermolecular C-C distance is always the same (about 2.6 A) once collective motions are taken into account, and it is independent of the pressure and temperature conditions. This conclusion is supported by first-principles molecular-dynamics simulations. This is a clear demonstration of the role of lattice phonons in driving the reactivity in the crystalline phase by fine-tuning of the nearest-neighbour distances. The knowledge of the critical C-C distance can be crucial in planning solid-state reactions at moderate pressure.
authors.affiliation: LENS, European Laboratory for Non-Linear Spectroscopy and INFM, Via Carrara 1, I-50019 Sesto Fiorentino, Firenze, Italy.
authors.forename: Lucia
authors.initials: L
authors.lastname: Ciabini
authors.forename: Mario
authors.initials: M
authors.lastname: Santoro
authors.forename: Federico A
authors.initials: FA
authors.lastname: Gorelli
authors.forename: Roberto
authors.initials: R
authors.lastname: Bini
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Schettino
authors.forename: Simone
authors.initials: S
authors.lastname: Raugei