High-Pressure Optical Properties and Chemical Stability of Picene

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• 作者：Samuele Fanetti ; Margherita Citroni ; Lorenzo Malavasi ; Gianluca A. Artioli ; Paolo Postorino ; Roberto Bini
• 刊名：The Journal of Physical Chemistry C
• 出版年：2013
• 出版时间：March 14, 2013
• 年：2013
• 卷：117
• 期：10
• 页码：5343-5351
• 全文大小：416K
• 年卷期：v.117,no.10(March 14, 2013)
• ISSN：1932-7455

文摘

Picene is a polycyclic aromatic hydrocarbon belonging to the class of phenacenes which have been recently found to behave as high-temperature superconductors upon alkali metal doping. The electronic properties of organic crystals can be finely and largely modified by the density changes obtained by the application of an external pressure. In this work, the role of pressure in tuning the optical properties of crystalline picene has been investigated from room conditions up to 15 GPa through the measurement of UV鈥搗isible absorption spectra, two-photon excitation profiles, and one- and two-photon excited fluorescence spectra in a diamond anvil cell. The pressure dependence of the optical band gap was determined, and the frequencies of several vibronic bands belonging to electronic transitions from the ground state (S₀) to the four lowest-energy excited singlet states (S₁ to S₄) were determined as a function of pressure. We evidence a very different density dependence of the transition energy of S₀ 鈫?S₁, which undergoes a remarkable red shift of 400 cm^鈥?/GPa, and of the transitions from S₀ to the higher excited states, which remain constant in the whole investigated range. This is consistent with a S₁ state of ¹L_a character in solid picene. The high-pressure chemical stability of solid picene was investigated through visible absorption and Fourier transform infrared spectroscopy (FTIR). A chemical transformation involving the bulk picene crystal occurs above 23 GPa, giving rise to a disordered material similar to the amorphous hydrogenated carbon obtained in the pressure-induced reactivity of benzene. The combination of electronic and vibrational data allows us to identify the presence of reaction intermediates at 10 GPa, preferentially forming at crystal defects.