The effect of high pressure on the structural stability of oxamide has been investigated in a diamond anvil cell by Raman spectroscopy up to ∼14.6 GPa and by angle-dispersive X-ray diffraction (ADXRD) up to ∼17.5 GPa. The discontinuity in Raman shifts around 9.6 GPa indicates a pressure-induced structural phase transition. This phase transition is confirmed by the change of ADXRD spectra with the symmetry transformation from P1 to P1. On total release of pressure, the diffraction pattern returns to its initial state, implying this transition is reversible. We discuss the pressure-induced variations in N-H stretching vibrations and the amide modes in Raman spectra and propose that this phase transition is attributed to the distortions of the hydrogen-bonded networks.
Searching for nontoxic and stable perovskite-like alternatives to lead-based halide perovskites for photovoltaic application is one urgent issue in photoelectricity science. Such exploration inevitably requires an effective method to accurately control both the crystalline and electronic structures. This work applies high pressure to narrow the band gap of perovskite-like organometal halide, [NH-(CH)-NH]CuCl (DABCuCl), through the crystalline-structure tuning. The band gap keeps decreasing below ∼12 GPa, involving the shrinkage and distortion of CuCl. Inorganic distortion determines both band-gap narrowing and phase transition between 6.4 and 10.5 GPa, and organic chains function as the spring cushion, evidenced by the structural transition at ∼0.8 GPa. The supporting function of organic chains protects DABCuCl from phase transition and amorphization, which also contributes to the sustaining band-gap narrowing. This work combines crystal structure and macroscopic property together and offers new strategies for the further design and synthesis of hybrid perovskite-like alternatives.
In situ high-pressure Raman spectroscopy and synchrotron
X-ray
diffraction (XRD) have been employed to investigate the behavior of
the energetic material urea nitrate ((NH2)2COH+·NO3
–, UN) up to the pressure
of ∼26 GPa. UN exhibits the typical supramolecular structure
with the uronium cation and nitrate anion held together by multiple
hydrogen bonds in the layer. The irreversible phase transition in
the range ∼9–15 GPa has been corroborated by experimental
results and is proposed to stem from rearrangements of hydrogen bonds.
Further analysis of XRD patterns indicates the new phase (phase II)
has Pc symmetry. The retrieved sample is ∼10.6%
smaller than the ambient phase (phase I) in volume owing to the transformation
from two-dimensional (2D) hydrogen-bonded networks to three-dimensional
(3D) ones. The mechanism for the phase transition involves the cooperativity
of noncovalent interactions under high pressure and distortions of
the layered structure. This work suggests high pressure is an efficient
technique to explore the performance of energetic materials, and to
synthesize new phases with high density.
The metastable wurtzite nanocrystals of CuGaS(2) have been synthesized through a facile and effective one-pot solvothermal approach. Through the Rietveld refinement on experimental X-ray diffraction patterns, we have unambiguously determined the structural parameters and the disordered nature of this wurtzite phase. The metastability of wurtzite structure with respect to the stable chalcopyrite structure was testified by a precise theoretical total energy calculation. Subsequent high-pressure experiments were performed to establish the isothermal phase stability of this wurtzite phase in the pressure range of 0-15.9 GPa, above which another disordered rock salt phase crystallized and remained stable up to 30.3 GPa, the highest pressure studied. Upon release of pressure, the sample was irreversible and intriguingly converted into the energetically more favorable and ordered chalcopyrite structure as revealed by the synchrotron X-ray diffraction and the high-resolution transmission electron microscopic measurements. The observed phase transitions were rationalized by first-principles calculations. The current research surely establishes a novel phase transition sequence of disorder → disorder → order, where pressure has played a significant role in effectively tuning stabilities of these different phases.
We report the high-pressure response of guanidinium methanesulfonate (C(NH(2))(3)(+)·CH(3)SO(3)(-), GMS) using in situ Raman spectroscopy and synchrotron X-ray diffraction (XRD) techniques up to the pressures of ~11 GPa. GMS exhibits the representative supramolecular structure of two-dimensional (2D) hydrogen-bonded bilayered motifs under ambient conditions. On the basis of the experimental results, two phase transitions were identified at 0.6 and 1.5 GPa, respectively. The first phase transition, which shows the reconstructive feature, is ascribed to the rearrangements of hydrogen-bonded networks, resulting in the symmetry transformation from C2/m to Pnma. The second one proves to be associated with local distortions of methyl groups, accompanied by the symmetry transformation from Pnma to Pna2(1). The cooperativity of hydrogen bonding, electrostatic, and van der Waals interactions, as well as mechanisms for the phase transitions is discussed by means of the local nature of the structure.
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