Solid-state optical absorption from optimally tuned time-dependent range-separated hybrid density functional theory

We present a framework for obtaining reliable solid-state charge and optical excitations and spectra from optimally tuned range-separated hybrid density functional theory. The approach, which is fully couched within the formal framework of generalized Kohn-Sham theory, allows for the accurate prediction of exciton binding energies. We demonstrate our approach through first principles calculations of one- and two-particle excitations in pentacene, a molecular semiconducting crystal, where our work is in excellent agreement with experiments and prior computations. We further show that with one adjustable parameter, set to produce the known band gap, this method accurately predicts band structures and optical spectra of silicon and lithium fluoride, prototypical covalent and ionic solids. Our findings indicate that for a broad range of extended bulk systems, this method may provide a computationally inexpensive alternative to many-body perturbation theory, opening the door to studies of materials of increasing size and complexity.

Solid-state chemistry of high-temperature oxide superconductors:The experimental situation

High-temperature superconductivity in oxides of the type(La, Ln)2?xBax(Sr)xCuO4, Y(Ln)Ba2Cu3O7??, La3?xBa3+xCu6O14, and related systems is discussed with emphasis on aspects related to experimental solid-state chemistry. All of these oxides possess perovskite-related structures. Oxygen-excess and La-deficient La2CuO4 also exhibit superconductivity in the 20�40 K just as La2?xBax(Srx)CuO4; these oxides are orthorhombic in the superconductivity phase. The crucial role of oxygen stoichiometry in the superconductivity ofYBa2Cu3O7?? (Tc = 95 ± 5K) is examined; this oxide remains orthorhombic up to ? ? 0.6 and becomes tetragonal and nonsuperconducting beyond this value of ?. Oxygen stoichiometry in this and related oxides has to be understood in terms of structure and disorder. The structure of La3?xBa3+xCu6O14 is related to that of YBa2Cu3O7, the orthorhombic structure manifesting itself when the population of O1 oxygens (along the Cusingle bondOsingle bondCu chains) is preponderant compared to that of O5 oxygens (along thea-axis); nearly equal populations of O1 and O5 sites give rise to the tetragonal structure. A transition from a high-Tc (95 K) superconductivity regime to a low-Tc (not, vert, similar60 K) regime occurs in YBa2Cu3O7?? accompanying a change in ?. There is no evidence for Cu3+ in these nominally mixed valent copper oxides. Instead, holes are present on oxygens giving rise to O? or O2?2 species, the concentration of these species increasing with the lowering of temperature. Certain interesting aspects of the superconducting oxides such as domain or twin boundaries, Raman spectra, microwave absorption, and anomalous high-temperature resistivity drops are presented along with the important material parameters. Preparative aspects of the superconducting oxides are briefly discussed. Phase transitions seem to occur atTc as well as at not, vert, similar240 K in YBa2Cu3O7.

Photophysical, electrochemical and solid state properties of diketopyrrolopyrrole based molecular materials: importance of the donor group

Diketopyrrolopyrrole (DPP) based molecular semiconductors have emerged as promising materials for high performance active layers in organic solar cells. It is imperative to comprehend the origin of such a property by investigating the fundamental structure property correlation. In this report we have investigated the role of the donor group in DPP based donor-acceptor- donor (D-A-D) structure to govern the solid state, photophysical and electrochemical properties. We have prepared three derivatives of DPP with varying strengths of the donor groups, such as phenyl (PDPP-Hex), thiophene (TDPP-Hex) and selenophene (SeDPP-Hex). The influence of the donor units on the solid state packing was studied by single crystal X-ray diffraction. The photophysical, electrochemical and density functional theory ( DFT) results were combined to elucidate the structural and electronic properties of three DPP derivatives. We found that these DPP derivatives crystallized in the monoclinic space group P21/c and show herringbone packing in the crystal lattice. The derivatives exhibit weak p-p stacking interactions as two neighboring molecules slip away from each other with varied torsional angles at the donor units. The high torsional angle of 32 degrees ( PDPP-Hex) between the phenyl and lactam ring results in weak intramolecular interactions between the donor and acceptor, while TDPP-Hex and SeDPP-Hex show lower torsional angles of 9 degrees and 12 degrees with a strong overlap between the donor and acceptor units. The photophysical properties reveal that PDPP-Hex exhibits a high Stokes shift of 0.32 eV and SeDPP- Hex shows a high molar absorption co-efficient of 33 600 L mol -1 1 cm -1 1 with a low band gap of similar to 2.2 eV. The electrochemical studies of SeDPP- Hex indicate the pronounced effect of selenium in stabilizing the LUMO energy levels and this further emphasizes the importance of chalcogens in developing new n-type organic semiconductors for optoelectronic devices.

Biomimetic molecular organization of naphthalene diimide in the solid state: tunable (chiro-) optical, viscoelastic and nanoscale properties

The interfacing of aromatic molecules with biomolecules to design functional molecular materials is a promising area of research. Intermolecular interactions determine the performance of these materials and therefore, precise control over the molecular organization is necessary to improve functional properties. Herein we describe the tunable biomimetic molecular engineering of a promising n-type organic semiconductor, naphthalene diimide (NDI), in the solid state by introducing minute structural mutations in the form of amino acids with variable Ca-functionality. For the first time we could achieve all four possible crystal packing modes, namely cofacial, brickwork, herringbone and slipped stacks of the NDI system. Furthermore, amino acid conjugated NDIs exhibit ultrasonication induced organogels with tunable visco-elastic and temperature responsive emission properties. The amino acid-NDI conjugates self-assemble into 0D nanospheres and 1D nanofibers in their gel state while the ethylamine-NDI conjugate forms 2D sheets from its solution. Photophysical studies indicated the remarkable influence of molecular ordering on the absorption and fluorescence properties of NDIs. Interestingly, the circular dichroism (CD) and X-ray diffraction (XRD) studies revealed the existence of helical ordering of NDIs in both solution and solid state. The chiral amino acids and their conformations with respect to the central NDI core are found to influence the nature of the helical organization of NDIs. Consequently, the origin of the preferential handedness in the helical organization is attributed to transcription of chiral information from the amino acid to the NDI core. On account of these unique properties, the materials derived from NDI-conjugates might find a wide range of future interdisciplinary applications from materials to biomedicine.

Efficient Solid-State Light-Emitting CuCdS Nanocrystals Synthesized in Air

Semiconductor nanocrystals (NCs) possess high photoluminescence (PL) typically in the solution phase. In contrary, PL rapidly quenches in the solid state. Efficient solid state luminescence can be achieved by inducing a large Stokes shift. Here we report on a novel synthesis of compositionally controlled CuCdS NCs in air avoiding the usual complexity of using inert atmosphere. These NCs show long-range color tunability over the entire visible range with a remarkable Stokes shift up to about 1.25eV. Overcoating the NCs leads to a high solid-state PL quantum yield (QY) of ca. 55% measured by using an integrating sphere. Unique charge carrier recombination mechanisms have been recognized from the NCs, which are correlated to the internal NC structure probed by using extended X-ray absorption fine structure (EXAFS) spectroscopy. EXAFS measurements show a Cu-rich surface and Cd-rich interior with 46% Cu-I being randomly distributed within 84% of the NC volume creating additional transition states for PL. Color-tunable solid-state luminescence remains stable in air enabling fabrication of light-emitting diodes (LEDs).

Effects of heat exchanger design on the performance of a solid state hydrogen storage device

Heat exchanger design plays a significant role in the performance of solid state hydrogen storage device. In the present study, a cylindrical hydrogen storage device with an embedded annular heat exchanger tube with radial circular copper fins, is considered. A 3-D mathematical model of the storage device is developed to investigate the sorption performance of metal hydride (MH). A prototype of the device is fabricated for 1 kg of MH alloy, LaNi5, and tested at constant supply pressure of hydrogen, validating the simulation results. Absorption characteristics of storage device have been examined by varying different operating parameters such as hydrogen supply pressure and cooling fluid temperature and velocity. Absorption process is completed in 18 min when these parameters are 15 bar, 298 K and 1 m/s respectively. A study of geometric parameters of copper fins (such as perforation, number and thickness of fin) has been carried out to investigate their effects on absorption process. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Sizable photocurrent and emission from solid state devices based on CdS nanoparticles

CdS nanoparticles exhibit size dependent optical and electrical properties. We report here the photocurrent and I-V characteristic studies of CdS nanoparticle devices. A sizable short circuit photocurrent was observed in the detection range governed by the size of the clusters. We speculate on the mechanisms leading to the photocurrent and emission in these nanometer scale systems.

Preparation of lamellar and hexagonal forms of mesoporous silica and zirconiaby the neutral amine route: lamellar-hexagonal transformation in the solid state

The chain length of the surfactant and the solvent composition are two of the factors that determine whether the lamellar or the hexagonal form of mesoporous SiO2 (or ZrO2) is formed by the neutral amine route; a lamellar-hexagonal transformation occurs on removal of the amine from the former.

Unusual photodimerization of 7-fluoro-4-methylcoumarin and 6-fluoro-4-methylcoumarin in the solid state

Photodimerization of 7-fluoro-4-methylcoumarin 1 is topochemical while 6-fluoro-4-methylcoumarin 2 does not lead to the expected product based on the topochemical principles. Compound 1 yield an anti-MT photodimer with a lower dimer conversion while compound 2 results in a syn-HH photodimer. The packing features of 1, 2 and 2a (the photodimer of 2) have been unequivocally established by single crystal X-ray diffraction studies. The rationale for the significant lower dimer conversion in 1 is provided. The defect induced dimerization reaction in 2 as a function of temperature is analyzed which verifies that the reaction proceeds with an induction period. The details of the interactions involving fluorine are analyzed.

Solid state stacked trimers of 1,10-phenanthroline in a supramolecular tubular motif of C-methyl calix[4]resorcinarene

The self-assembly of bidentate ligand, 1,10-phenanthroline with C-methyl calix[4]resorcinarene (CMCR) in presence of coumarin results in a unique trimer stacking arrangement of phenanthroline molecules in a nanotubular motif generated by the supramolecular assembly of the host.

A thermal molecular migration in the solid-state - structures of isomeric 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1h-1,2,3-triazole (yellow form i) and 4-(2,6-dichlorophenyl)-5-(2-nitroanilino)-2h-1,2,3-triazole (red form-ii), c14h9cl2n5o2

Yellow form (I): Mr= 350.09, monoclinic, P2Jn, Z--4, a=9.525(1), b=14.762(1), c= 11.268(1),/t, fl= 107.82 (1) o , V= 1508.3 A 3 , Din(flotation in aqueous KI)= 1.539 (2), D x= 1.541 (2) g cm -3, #(Cu Ka, 2 = 1.5418 A) = 40.58 cm -~, F(000) = 712, T= 293 K, R = 8.8% for 2054 significant refections. Red form (II): Mr= 350.09, triclinic, Pi, Z=2, a=9.796(2), b= 10.750 (2), c= 7.421 (1)A, a= 95.29 (2), fl= 0108-2701/84/111901-05501.50 70.18 (1), y = 92-.76 (2) °, V= 731.9 A 3, Din(flotation in KI) = 1.585 (3), D x = 1.588 (3) g cm -3, ~t(Cu Ka, 2 = 1.5418/~) = 40.58 cm -1, F(000) = 356, T=293 K, R = 5.8% for 1866 significant reflections. There are no unusual bond distances or angles. The triazole and two phenyl rings are planar. On the basis of packing considerations the possibility of intermolecular interactions playing a role in the reactivity of the starting material is ruled out.

Nanopatterning by solid-state dewetting on reconstructed ceramic surfaces

We demonstrate ordered array formation of Au nanoparticles by controlled solid-state dewetting of a metal film on stepped alumina substrates. In situ transmission electron microscopy studies reveal that the dewetting process starts with nucleation of ordered dry regions on the substrate. The chemical potential difference between concave and convex surface regions induces anisotropic metal diffusion leading to the formation of nanowires in the valleys. The nanowires fragment due to Rayleigh instability forming arrays of metal nanoparticles on the substrate. The length scale of reconstruction relative to the starting film thickness is an important parameter in controlling the spatial order of the nanoparticles.

Reversible photodimerization of phenylbutadienes in the solid state

Based on x-ray crystallographic studies, it is shown that crystal chemical factors govern the reversible photodimerization of phenylbutadienes in the solid state.

Solid-state Thermal Polymerization of Sodium Acrylate

Initiation and propagation processes in thermally initiated solid-state polymerization of sodiumvacrylate have been studied. The kinetics of initiation, followed with the electron spin resonancev technique, leads to an activation energy E of 28.8 kcal/mol, which is attributed to the formation of dimeric radicals. The activation energy of 16 f 1 kcaVmol obtained for the solid-state polymerization of sodium acrylate by chemical analysis and differential scanning calorimetry has been attributed to the propagation process.

Thermal polymerization of acrylamide in the solid state

The role of imperfections in thermal polymerization of acrylamide in the solid state was studied. The polymer yield and the degree of polymerization are highly dependent on the particle size and on the pressure to which the monomer is subjected prior to polymerization reaction. There is an enhancement in the rate of polymerization in air unlike in the case of radiation-induced polymerization. Thermal polymerization of acrylamide in pelletized form results in the formation of water-soluble linear polymer and water-insoluble cross-linked product with the evolution of ammonia. The activation energy (E) values obtained in the present investigation reveal that basically there are two processes taking place, one with E = 34–36 kcal/mole, corresponding to the initiation process, and the other with E = 19 ± 3 kcal/more for the propagation process.