Quasistatic Disorder of NH路路路N Bonds and Elastic-Properties Relationship in 2-Phenylimidazole Crystals

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• 作者：Magdalena Sikora ; Piotr Bernatowicz ; Marek Szafra艅ski ; Andrzej Katrusiak
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：April 3, 2014
• 年：2014
• 卷：118
• 期：13
• 页码：7049-7056
• 全文大小：512K
• 年卷期：v.118,no.13(April 3, 2014)
• ISSN：1932-7455

文摘

The molecular aggregation in 2-phenylimidazole is analogous to that observed in the new class of NH路路路N bonded ferroelectrics and relaxors. Disordered H-atoms in NH路路路N hydrogen-bonded chains in the average crystal structure of 2-phenylimidazole persist to 100 K, but the relaxation time of this process is very long even above 340 K. Above 200 K, a gradual increase of the electric permittivity along chains testifies to the activation of dipolar fluctuations, associated with proton transfers in the quasistatic disordered chains. However, the chemical shifts of nitrogen atoms (equivalent according to the average crystal symmetry) remain clearly distinguished as protonated and unprotonated in ¹⁵N NMR spectra up to 340 K at least. The 2-phenylimidazole crystal exhibits an unusual negative-linear thermal expansion (NTE) in the entire 140鈥?40 K range, induced by subtle rotations of the NH路路路N bonded molecules. The NTE direction is the softest in the hydrostatically compressed crystal, which violates the inverse relationship rule of compression and thermal expansion. The crystal compression is monotonic, but clearly nonlinear, which is connected with the pressure enforced adjustments in the molecular packing between 0.1 MPa and 0.4 GPa, when small voids between molecules are eliminated.