The role of copper in the thermal conductivity of thermoelectric oxychalcogenides: do lone pairs matter?

Understanding the underlying mechanisms that suppress thermal conduction in solids is of paramount importance for the targeted design of materials for thermal management and thermoelectric energy conversion applications. Bismuth copper oxychalcogenides, BiOCuQ (Q = Se, Te), are highly crystalline thermoelectric materials with an unusually low lattice thermal conductivity of approx. 0.5 Wm-1K-1, a value normally found in amorphous materials. Here we unveil the origin of the unusual thermal transport properties of these phases. First principles calculations of the vibrational properties combined with analysis of in-situ neutron diffraction data, demonstrate that weak bonding of copper atoms within the structure leads to an unexpected vibrational mode at low frequencies, which is likely to be a major contributor to the low thermal conductivity of these materials. In addition, we show that anharmonicity and the large Grüneisen parameter in these oxychalcogenides are mainly related to the low frequency copper vibrations, rather than to the Bi3+ lone pairs.

Mixed-phase cloud physics and Southern Ocean cloud feedback in climate models

Increasing optical depth poleward of 45° is a robust response to warming in global climate models. Much of this cloud optical depth increase has been hypothesized to be due to transitions from ice-dominated to liquid-dominated mixed-phase cloud. In this study, the importance of liquid-ice partitioning for the optical depth feedback is quantified for 19 Coupled Model Intercomparison Project Phase 5 models. All models show a monotonic partitioning of ice and liquid as a function of temperature, but the temperature at which ice and liquid are equally mixed (the glaciation temperature) varies by as much as 40 K across models. Models that have a higher glaciation temperature are found to have a smaller climatological liquid water path (LWP) and condensed water path and experience a larger increase in LWP as the climate warms. The ice-liquid partitioning curve of each model may be used to calculate the response of LWP to warming. It is found that the repartitioning between ice and liquid in a warming climate contributes at least 20% to 80% of the increase in LWP as the climate warms, depending on model. Intermodel differences in the climatological partitioning between ice and liquid are estimated to contribute at least 20% to the intermodel spread in the high-latitude LWP response in the mixed-phase region poleward of 45°S. It is hypothesized that a more thorough evaluation and constraint of global climate model mixed-phase cloud parameterizations and validation of the total condensate and ice-liquid apportionment against observations will yield a substantial reduction in model uncertainty in the high-latitude cloud response to warming.