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Triggering dynamics of the high-pressure benzene amorphization

Nature Materials volume 6, pages 39–43 (2007)Cite this article

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 crystals1,2,3,4,5, 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 Å) 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.

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Figure 1: Detecting the onset of the reaction at 423 K.
Figure 2: Phase diagram and chemical-stability boundary of benzene.
Figure 3: Pressure evolution of nn C⋯C distances at 540 K.
Figure 4: Ab initio molecular-dynamics simulation results.

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Acknowledgements

The European Union, under contract RII3-CT2003-506350, the Italian Ministero dell’Università e della Ricerca Scientifica e Tecnologica (MURST) and ‘Firenze Hydrolab’, through a grant by Ente Cassa di Risparmio di Firenze, supported this work. The authors gratefully acknowledge M. Mezouar and the staff of ID30 at ESRF for the X-ray diffraction measurements and the CINECA Supercomputing Centre (Bologna, Italy) for allocation of computer time.

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Authors and Affiliations

  1. LENS, European Laboratory for Non-Linear Spectroscopy and INFM, Via Carrara 1, I-50019 Sesto Fiorentino, Firenze, Italy

    Lucia Ciabini, Mario Santoro, Federico A. Gorelli, Roberto Bini & Vincenzo Schettino

  2. Dipartimento di Chimica dell’Università di Firenze, Via della Lastruccia 3, I-50019 Sesto Fiorentino, Firenze, Italy

    Lucia Ciabini, Roberto Bini & Vincenzo Schettino

  3. CRS-SOFT-INFM-CNR, Università di Roma La Sapienza, P.zza A. Moro 2, I-00185, Roma, Italy

    Mario Santoro & Federico A. Gorelli

  4. International School for Advanced Studies (SISSA/ISAS) and INFM-DEMOCRITOS MOdeling Center for Research In aTOmistic Simulation, Via Beirut 2-4, 34014, Trieste, Italy

    Simone Raugei

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  1. Lucia Ciabini
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Correspondence to Roberto Bini.

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Ciabini, L., Santoro, M., Gorelli, F. et al. Triggering dynamics of the high-pressure benzene amorphization. Nature Mater 6, 39–43 (2007). https://doi.org/10.1038/nmat1803

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