Role of excited electronic states in the high-pressure amorphization of benzene.

Abstract:

:High-pressure methods are increasingly used to produce new dense materials with unusual properties. Increasing efforts to understand the reaction mechanisms at the microscopic level, to set up and optimize synthetic approaches, are currently directed at carbon-based solids. A fundamental, but still unsolved, question concerns how the electronic excited states are involved in the high-pressure reactivity of molecular systems. Technical difficulties in such experiments include small sample dimensions and possible damage to the sample as a result of the absorption of intense laser fields. These experimental challenges make the direct characterization of the electronic properties as a function of pressure by linear and nonlinear optical spectroscopies up to several GPa a hard task. We report here the measurement of two-photon excitation spectra in a molecular crystal under pressure, up to 12 GPa in benzene, the archetypal aromatic system. Comparison between the pressure shift of the exciton line and the monomer fluorescence provides evidence for different compressibilities of the ground and first excited states. The formation of structural excimers occurs with increasing pressure involving molecules on equivalent crystal sites that are favorably arranged in a parallel configuration. These species represent the nucleation sites for the transformation of benzene into amorphous hydrogenated carbon. The present results provide a unified picture of the chemical reactivity of benzene at high pressure.

authors

Citroni M,Bini R,Foggi P,Schettino V

doi

10.1073/pnas.0802269105

subject

Has Abstract

pub_date

2008-06-03 00:00:00

pages

7658-63

issue

22

eissn

0027-8424

issn

1091-6490

pii

0802269105

journal_volume

105

pub_type

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