No abstract

A solid with larger sound speeds usually exhibits higher lattice thermal conductivity. Here, we report an exception that CuP2 has a quite large mean sound speed of 4155 m s−1, comparable to GaAs, but single crystals show very low lattice thermal conductivity of about 4 W m−1 K−1 at room temperature, one order of magnitude smaller than GaAs. To understand such a puzzling thermal transport behavior, we have thoroughly investigated the atomic structures and lattice dynamics by combining neutron scattering techniques with first-principles simulations. This compound crystallizes in a layered structure where Cu atoms forming dimers are sandwiched in between P atomic networks. In this work, we reveal that Cu atomic dimers vibrate as a rattling mode with frequency around 11 meV, which is manifested to be remarkably anharmonic and strongly scatters acoustic phonons to achieve the low lattice thermal conductivity.

Coupled potential energy surface for the F( 2 P) + CH 4 → HF + CH 3 entrance channel and quantum dynamics of the CH 4 · F

The discovery of colossal barocaloric effects in organic plastic crystals has significantly advanced the development of solid‐state refrigerant techniques. Adapting to the real application, a tradeoff of various barocaloric performances has to be achieved. Here, it is reported a novel plastic crystal system, that is, carboranes (C2B10H12), including three positional isomers: ortho‐carborane, meta‐carborane, and para‐carborane, which are characterized by C2v, C2v, D5d point groups, respectively. They all undergo an orthorhombic‐to‐tetragonal phase transition around room temperature. Compared to the previously reported organic plastic crystals, this system exhibits a combination of large pressure‐normalized entropy changes, the high‐pressure sensitivity of the transition temperature, small thermal hysteresis, and so forth. Their barocaloric performances are positional‐isomerism dependent, and the best performances are obtained in para‐carborane with maximum entropy changes of about 106.2 J kg−1 K−1 achieved under pressure changes below 30 MPa. This study not only suggests that carboranes would be a considerably promising working material for barocaloric refrigeration at room temperature but also indicates that delicate tuning of molecular isomerism is an effective strategy to enhance barocaloric performances.

One of the greatest obstacles to the real application of solid-state refrigeration is the huge driving fields. Here, we report a giant barocaloric effect in inorganic NH4I with reversible entropy changes of $$\Delta {S}_{{P}_{0}\to P}^{{{\max }}}$$ Δ S P 0 → P max ∼71 J K−1 kg−1 around room temperature, associated with a structural phase transition. The phase transition temperature, Tt, varies dramatically with pressure at a rate of dTt/dP ∼0.79 K MPa−1, which leads to a very small saturation driving pressure of ΔP ∼40 MPa, an extremely large barocaloric strength of $$\left|\Delta {S}_{{P}_{0}\to P}^{{{\max }}}/\Delta P\right|$$ Δ S P 0 → P max / Δ P ∼1.78 J K−1 kg−1 MPa−1, as well as a broad temperature span of ∼41 K under 80 MPa. Comprehensive characterizations of the crystal structures and atomic dynamics by neutron scattering reveal that a strong reorientation-vibration coupling is responsible for the large pressure sensitivity of Tt. This work is expected to advance the practical application of barocaloric refrigeration.

Full-dimensional coupled-channel quantum scattering and quasi-classical trajectory calculations have been carried out and analyzed to unravel the mode specific dynamics in the H + SH → H + HS reaction employing two different accurate neural network representations of an ab initio global potential energy surface at the coupled cluster level. Strong mode selectivity was found and partially rationalized by the sudden vector projection model. Specifically, the vibrational excitation of H remarkably enhances the reactivity while its rotational excitation only slightly promotes the reaction. On the other hand, the reactant SH acts as a good spectator, whose vibrational and rotational excitations have a negligible effect on the reaction.

The hydrogen abstraction reactions of the hydroxyl radical with alkanes play an important role in combustion chemistry and atmospheric chemistry. However, site-specific reaction constants are difficult to obtain experimentally and theoretically. Recently, machine learning has proved its ability to predict chemical properties. In this work, a machine learning approach is developed to predict the temperature-dependent site-specific rate constants of the title reactions. Multilayered neural network (NN) models are developed by training the site-specific rate constants of 11 reactions, and several schemes are designed to improve the prediction accuracy. The results show that the proposed NN models are robust in predicting the site-specific and overall rate constants.

We report the observation of the giant topological Hall effect near room temperature in a complex noncollinear ferromagnet NdMn2Ge2 single crystal. Three successive magnetic transitions are observed below 400 K, including a spin reorientation transition at TSR = 215 K. The complex noncollinear magnetic structures give rise to anomalous transport behaviors. When the current flows along the a axis and the magnetic field is applied along the c axis, the anomalous Hall effect is observed, which is found to be dominated by the skew scattering mechanism. Strikingly, a giant topological Hall effect appears in a wide temperature range, which stems from the noncollinear spin configuration with finite scalar spin chirality. The topological Hall resistivity reaches the maximum of −1.35 μΩ cm at 300 K and drops slightly with temperature until below TSR. These results suggest that the NdMn2Ge2 single crystal would be a promising topological material for spintronic applications at room temperature.