arXiv subjects

Guanqun Cai

Publications and source records attributed to Guanqun Cai.

7 recordsLinked to original sources

arXiv2026

Hidden in-plane long-range order in an amorphized crystal

Solid materials are commonly classified as crystalline or amorphous based on the presence or absence of long-range order.Metal-organic frameworks (MOFs), like other solids,also display markedly different properties and functions in these two phases. Here, we identify a previously unrecognized structural state that retains long-range in-plane translational order while losing order along the stacking direction. Hypothesized since 1941 but not experimentally verified, this intermediate phase emerges in a crystalline MOFs via controlled thermal desolvation, which selectively disrupts the intrinsically weak interlayer interactions while preserving macroscopic structural coherence. Although the resulting material appears amorphous under conventional characterization, systematic synchrotron PXRD, total X-ray scattering, and low-dose high resolution TEM reveal clear in-plane periodicity. This material spontaneously delaminates in water into uniform, high-quality two-dimensional crystalline nanosheets, forming stable colloidal suspensions and exhibiting superlubricity comparable to graphene - but at less than 0.1% of the production cost. Our discovery finds a missing link within the long-standing crystalline-amorphous dichotomy, while providing an inherently scalable route to high-quality 2D crystals, and offering a conceptual and practical advance in phase engineering.

cond-mat.mtrl-sci↗

arXiv2022

Pressure dependence of atomic dynamics in barocaloric ammonium sulfate: II. Vibrations

Ammonium sulfate is a giant inverse barocaloric material that is cheaply and commercially available. Exploiting its potential for cooling applications requires an understanding of the mechanism driving the entropy change. Here we report an investigation by inelastic neutron scattering and density functional theory of the phonons under working conditions of temperature and pressure. We find excellent agreement between the experimental and calculated results. The ammonium librational modes that are crucial to the entropy change are identifiable by their negative Grüneisen parameter. Our results connect the differences in structure across the phase transition to those in the atomic dynamics, suggesting a route towards designing new caloric materials.

cond-mat.mtrl-sci↗

arXiv2022

Origin of the large entropy change in the molecular caloric and ferroelectric ammonium sulfate

The deceptively simple inorganic salt ammonium sulfate undergoes a ferroelectric phase transition associated with a very large entropy change and both electrocaloric and barocaloric functionality. While the structural origins of the electrical polarisation are now well established, those of the entropy change have been controversial for over fifty years. This question is resolved here using a combination of DFT phonon calculations with inelastic neutron scattering under variable temperature and pressure, supported by complementary total and quasielastic neutron scattering experiments. A simple model of the entropy in which each molecular ion is disordered across the mirror plane in the high symmetry phase, although widely used in the literature, proves to be untenable. Instead, the entropy arises from low-frequency librations of ammonium ions in this phase, with harmonic terms that are very small or even negative. These results suggest that, in the search for molecular materials with functionality derived from large entropy changes, vibrational entropy arising from broad energy minima is likely to be just as important as configurational entropy arising from crystallographic disorder.

cond-mat.mtrl-sci↗

arXiv2022

Pressure dependence of atomic dynamics in barocaloric ammonium sulfate: I. Rotations

Solid-state cooling using barocaloric materials is a promising avenue for eco-friendly, inexpensive and highly efficient cooling. To design barocaloric compounds ready for deployment, it is essential to understand their thermodynamic behaviour under working conditions. To this end, we have studied the rotational dynamics in the molecular-ionic crystal ammonium sulfate under pressure, providing detailed insight into the origin of its large barocaloric effect. Using quasielastic neutron scattering experiments, we show that rotation of the ammonium cations is facilitated by pressure in the low-entropy phase, with the rotational "hopping" motion increasing in frequency as the pressure-induced phase transition is approached. We explain this unusual behaviour in terms of the competing hydrogen-bond networks represented by the two phases. This work includes the first results of a recently developed low-background, high-pressure gas cell for neutron scattering, showcasing its power in obtaining high-precision measurements of molecular dynamics under pressure.

cond-mat.mtrl-sci↗

arXiv2021

Atomic structure of the continuous random network of amorphous C[(C6H4)2]2, PAF-1

We demonstrate that the amorphous material PAF-1, C[(C6H4)2]2, forms a continuous random network in which tetrahedral carbon sites are connected by 4,4'-biphenyl linkers. Experimental neutron total scattering measurements on deuterated, hydrogenous, and null-scattering samples agree with molecular dynamics simulations based on this model. From the MD model, we are able for the first time to interrogate the atomistic structure. The small-angle scattering is consistent with Porod scattering from particle surfaces, of the form Q^{-4}, where Q is the scattering vector. We measure a distinct peak in the scattering at Q = 0.45 Å^{-1}, corresponding to the first sharp diffraction peak in amorphous silica, which indicates the structural analogy between these two amorphous tetrahedral networks.

cond-mat.dis-nn↗

arXiv2020

Colossal pressure-induced softening in scandium fluoride

The counter-intuitive phenomenon of pressure-induced softening in materials is likely to be caused by the same dynamical behaviour that produces negative thermal expansion. Through a combination of molecular dynamics simulation on an idealised model and neutron diffraction at variable temperature and pressure, we show the existence of extraordinary and unprecedented pressure-induced softening in the negative thermal expansion material scandium fluoride, ScF$_3$, with values of the pressure-derivative of the bulk modulus $B$, $B^\prime = \partial B / \partial P$, reaching as low as $-40 \pm 1$.

cond-mat.mtrl-sci↗

arXiv2018

Hydrogen-bond-mediated structural variation of metal guanidinium formate hybrid perovskites with unit cell volume

The hybrid perovskites are coordination frameworks with the same topology as the inorganic perovskites, but with properties driven by different chemistry, including host-framework hydrogen bonding. Like the inorganic perovskites, these materials exhibit many different phases, including structures with potentially exploitable functionality. However, far less is known about their behaviour under pressure. We have studied the structures of of manganese and cobalt guanidinium formate under pressure using single-crystal X-ray and powder neutron diffraction. Remarkably, when pressure reduces these materials' volume, they transform to a phase isostructural to cadmium guanidinium formate, which has an larger volume. Using DFT calculations, we show that this counterintuitive behaviour depends on the hydrogen-bonded network of guanidinium ions, which act as struts protecting the metal formate framework against compression. Our results demonstrate more generally that engineering desirable crystal structures in the hybrid perovskites will depend on achieving suitable host-guest hydrogen-bonding geometries.

cond-mat.mtrl-sci↗