Range-separated hybrid functionals along with global hybrids and pure density functionals have been employed to calculate geometries, ionization energies (IP)s, electron affinities (EA)s, and excitation energies of neutral and oxidized polyenes, thiophene, and furan oligomers. Long-range correction with 100% HF exchange solves the problem of density functional theory with incorrect chain length dependence of IPs and energy gaps. There is a possibility of overcorrection, if the short-range part of the functional with no or low HF exchange is too small. The wB97XD functional with 22% of HF exchange in the short-range and a range-separation parameter of 0.2 seems to be just right for conjugated systems at all chain lengths. The wB97XD functional additionally produces negative orbital energies in very good agreement with IPs and EAs. With correct orbital energies, band gaps correspond to transport gaps (Et) and not to optical gaps (Eg). Et is much larger than Eg in the gas phase, but the difference is significantly smaller in the solid state. The accuracy of the negative orbital energies is good down to about 30 eV so that valence and innervalence PE spectra can be modeled. wB97XD is therefore suitable for calculating band structures of conjugated polymers employing orbital energies.

Solar-driven thermochemical water splitting using non-stoichiometric oxides has emerged as an attractive technology for solar fuel production. The most widely considered oxide for this purpose is ceria, but the extreme temperatures required to achieve suitable levels of reduction introduce challenges in reactor design and operation, leading to efficiency penalties. Here, we provide a quantitative assessment of the thermodynamic and kinetic properties of La 1Àx Sr x MnO 3Àd perovskites, targeted for a reduced temperature operation of thermochemical water splitting. Sr-doping into lanthanum manganite increases the thermodynamic fuel production capacity, which reaches 9 ml g À1 for 0.

Mesoporous metal titanates are very important class of materials for clean energy applications, specifically transition metal titanates and lithium titanates. The molten salt assisted self-assembly (MASA) process offers a new synthetic route to produce mesoporous metal titanate thin films. The process is conducted as follows: first a clear solution that contains two solvents (namely the hydrated salt (Co(NO 3 ) 2 · 6H 2 O or Mn(NO 3 ) 2 ·6H 2 O, or LiNO 3 ·xH 2 O, and ethanol), two surfactants (cethyltrimethylammonium bromide, CTAB, and 10-lauryl ether, C 12 EO 10 ), an acid and titanium source (titanium tetrabutoxide, TTB) is prepared and then spin or spray coated over a substrate to form a thin or thick lyotropic liquid crystalline (LLC) film, respectively. Finally, the films are converted into transparent spongy mesoporous metal titanates by a fast calcination step. Three mesoporous metal titanates (namely, CoTiO 3 , MnTiO 3 , and Li 4 Ti 5 O 12 ) have been successfully synthesized and structurally/thermally characterized using microscopy, spectroscopy, diffraction, and thermal techniques. The mesoporous cobalt and manganese titanates are stable up to 500°C and collapse at around 550°C into nanocrystalline Co 3 O 4 − TiO 2 and Mn 2 O 3 −TiO 2 ; however, lithium titanate is stable up to 550°C and crystalline even at 350°C. The crystallinity and pore size of these titanates can be adjusted by simply controlling the annealing and/or calcination temperatures. ■ INTRODUCTIONThe melting point of metal salts can be reduced significantly in a confined space -known as the confinement effect -such that they may act as solvents in a self-assembly process.1 Organizing surfactants into lyotropic liquid crystalline (LLC) mesophases by using molten salts can be beneficial in the production of new materials for clean energy applications.2,3 Recently, we have demonstrated that the molten phase of salts can be used as a solvent in the synthesis of mesoporus metal oxide modified silica 2 as well as titania. 3 This process was introduced as molten salt assisted self-assembly (MASA).2,3 The MASA is a useful process in producing materials that are difficult to produce using known synthesis techniques, and it can be regarded as a new synthetic route. Two solvents and two surfactants are needed in this self-assembly process. The first solvent is volatile and is used to homogenize the mixture of the ingredients to produce a clear solution, 2,3 and the second solvent is a salt, which organizes the mixture into an LLC mesophase upon evaporation of the first one. 3 Simply, a clear solution of a mixture of all the ingredients (salt, surfactants, water (or ethanol), polymerizing agent) can be spin coated over a substrate to form a thin film. Further polymerization of the polymerizing component (silica or titania source) takes place in the self-assembled soft media. The MASA process allows for efficient and homogeneous contact between the polymerizing silica or titania and the salt ions. The spin coated fresh samples are usually ...