Thermodynamics and collective modes in hydrogen-bonded fluids.

The thermodynamics of liquids and supercritical fluids is notorious for eluding a general theory, as can be done for crystalline solids on the basis of phonons and crystal symmetry. The extension of solid state notions, such as configurational entropy and phonons, to the liquid state remains an intriguing but challenging topic. This is particularly true for liquids, such as water, whose many structural anomalies give it unique properties. Here, for simple fluids, we specify the thermodynamics across the liquid, supercritical, and gaseous states using the spectrum of propagating phonons, thereby determining the non-ideal entropy of the fluid using a single parameter arising from this phonon spectrum. This identifies a marked distinction between these "simple" fluids and hydrogen bonded fluids whose non-ideal entropy cannot be determined by the phonon spectrum alone. We relate this phonon theory of thermodynamics to the previously observed excess entropy scaling in liquids and how the phonon spectrum creates corresponding states across the fluid phase diagram. Although these phenomena are closely related, there remain some differences, in practice, between excess entropy scaling and the similar scaling seen due to phonon thermodynamics. These results provide important theoretical understanding to supercritical fluids, whose properties are still poorly understood despite widespread deployment in environmental and energy applications.

Microscopic Structure of Liquid Nitric Oxide.

The microscopic structure of nitric oxide is investigated using neutron scattering experiments. The measurements are performed at various temperatures between 120 and 144 K and at pressures between 1.1 and 9 bar. Using the technique of empirical potential structure refinement (EPSR), our results show that the dimer is the main form, around 80%, of nitric oxide in the liquid phase at 120 K, but the degree of dissociation to monomers increases with increasing temperature. The reported degree of dissociation of dimers, and its trend with increasing temperature, is consistent with earlier measurements and studies. It is also shown that nonplanar dimers are not inconsistent with the diffraction data and that the possibility of nitric oxide molecules forming longer oligomers, consisting of bonded nitrogen atoms along the backbone, cannot be ruled out in the liquid. A molecular dynamics simulation is used to compare the present EPSR simulations with an earlier proposed intermolecular potential for the liquid.

Double universality of the transition in the supercritical state.

Universality aids consistent understanding of physical properties and states of matter where a theory predicts how a property of a phase (solid, liquid, and gas) changes with temperature or pressure. Here, we show that the matter above the critical point has a remarkable double universality. The first universality is the transition between the liquid-like and gas-like states seen in the crossover of the specific heat on the dynamical length with a fixed inversion point. The second universality is the operation of this effect in many supercritical fluids, including N2, CO2, Pb, H2O, and Ar. Despite different structure and chemical bonding, the transition has the same fixed inversion point deep in the supercritical state. This advances our understanding of the supercritical state previously considered to be a featureless area on the phase diagram and a theoretical guide for improved deployment of supercritical fluids in green and environmental applications.

Stochastic thermodynamics in a non-Markovian dynamical system.

The developing field of stochastic thermodynamics extends concepts of macroscopic thermodynamics such as entropy production and work to the microscopic level of individual trajectories taken by a system through phase space. The scheme involves coupling the system to an environment-typically a source of Markovian noise that affects the dynamics of the system. Here we extend this framework to consider a non-Markovian environment, one whose dynamics have memory and which create additional correlations with the system variables, and illustrate this with a selection of simple examples. Such an environment produces a rich variety of behavior. In particular, for a case of thermal relaxation, the distributions of entropy produced under the non-Markovian dynamics differ from the equivalent case of Markovian dynamics only by a delay time. When a time-dependent external work protocol is turned on, the system's correlations with the environment can either assist or hinder its approach to equilibrium, and affect its production of entropy, depending on the coupling strength between the system and environment.

Experimental and modeling evidence for structural crossover in supercritical CO_{2}.

The physics of supercritical states is understood to a much lesser degree compared to subcritical liquids. Carbon dioxide, in particular, has been intensely studied, yet little is known about the supercritical part of its phase diagram. Here, we combine neutron scattering experiments and molecular dynamics simulations and demonstrate the structural crossover at the Frenkel line. The crossover is seen at pressures as high as 14 times the critical pressure and is evidenced by changes of the main features of the structure factor and pair distribution functions.