The Role of Anharmonicity in Hydrogen-Bonded Systems: The Case of Water Clusters

The nature of vibrational anharmonicity has been examined for the case of small water clusters using second-order vibrational perturbation theory (VPT2) applied on second-order Møller–Plesset perturbation theory (MP2) potential energy surfaces. Using a training set of 16 water clusters (H2O)n=2–6,8,9 with a total of 723 vibrational modes, we determined scaling factors that map the harmonic frequencies onto anharmonic ones. The intermolecular modes were found to be substantially more anharmonic than intramolecular bending and stretching modes. Due to the varying levels of anharmonicity of the intermolecular and intramolecular modes, different frequency scaling factors for each region were necessary to achieve the highest accuracy. Furthermore, new scaling factors for zero-point vibrational energies (ZPVE) and vibrational corrections to the enthalpy (ΔHvib) and the entropy (Svib) have been determined. All the scaling factors reported in this study are different from previous works in that they are intended for hydrogen-bonded systems, while others were built using experimental frequencies of covalently bonded systems. An application of our scaling factors to the vibrational frequencies of water dimer and thermodynamic functions of 11 larger water clusters highlights the importance of anharmonic effects in hydrogen-bonded systems.

Solar thermal decoupled water electrolysis process I: Proof of concept

A new concept for a solar thermal electrolytic process was developed for the production of H-2 from water. A metal oxide is reduced to a lower oxidation state in air with concentrated solar energy. The reduced oxide is then used either as an anode or solute for the electrolytic production of H-2 in either an aqueous acid or base solution. The presence of the reduced metal oxide as part of the electrolytic cell decreases the potential required for water electrolysis below the ideal 1.23 V required when H-2 and O-2 evolve at 1 bar and 298 K. During electrolysis, H-2 evolves at the cathode at 1 bar while the reduced metal oxide is returned to its original oxidation state, thus completing the H-2 production cycle. Ideal sunlight-to-hydrogen thermal efficiencies were established for three oxide systems: Fe2O3-Fe3O4, Co3O4-CoO, and Mn2O3-Mn3O4. The ideal efficiencies that include radiation heat loss are as high or higher than corresponding ideal values reported in the solar thermal chemistry literature. An exploratory experimental study for the iron oxide system confirmed that the electrolytic and thermal reduction steps occur in a laboratory scale environment.

Thermal Energy Storage for Solar Power Production

Solar energy is the most abundant persistent energy resource. It is also an intermittent one available for only a fraction of each day while the demand for electric power never ceases. To produce a significant amount of power at the utility scale, electricity generated from solar energy must be dispatchable and able to be supplied in response to variations in demand. This requires energy storage that serves to decouple the intermittent solar resource from the load and enables around-the-clock power production from solar energy. Practically, solar energy storage technologies must be efficient as any energy loss results in an increase in the amount of required collection hardware, the largest cost in a solar electric power system. Storing solar energy as heat has been shown to be an efficient, scalable, and relatively low-cost approach to providing dispatchable solar electricity. Concentrating solar power systems that include thermal energy storage (TES) use mirrors to focus sunlight onto a heat exchanger where it is converted to thermal energy that is carried away by a heat transfer fluid and used to drive a conventional thermal power cycle (e.g., steam power plant), or stored for later use. Several approaches to TES have been developed and can generally be categorized as either thermophysical (wherein energy is stored in a hot fluid or solid medium or by causing a phase change that can later be reversed to release heat) or thermochemical (in which energy is stored in chemical bonds requiring two or more reversible chemical reactions).