Experimental evidence for `carbon bonding' in the solid state from charge density analysis

The validity of the newly proposed `carbon bonding', an interaction where a carbon atom acts as an electrophilic site towards a variety of nucleophiles, has been investigated in the solid state. X-ray charge density analysis provides experimental evidence for this hitherto unexplored interaction and unravels its nature and strength.

Co-registration of speech production datasets from electromagnetic articulography and real-time magnetic resonance imaging

This paper describes a spatio-temporal registration approach for speech articulation data obtained from electromagnetic articulography (EMA) and real-time Magnetic Resonance Imaging (rtMRI). This is motivated by the potential for combining the complementary advantages of both types of data. The registration method is validated on EMA and rtMRI datasets obtained at different times, but using the same stimuli. The aligned corpus offers the advantages of high temporal resolution (from EMA) and a complete mid-sagittal view (from rtMRI). The co-registration also yields optimum placement of EMA sensors as articulatory landmarks on the magnetic resonance images, thus providing richer spatio-temporal information about articulatory dynamics. (C) 2014 Acoustical Society of America

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.

Symbiosis in Solid State Interconversion and Synthon Modularity in Hydroxybenzoic Acid-Hexamine Adducts

Systematic cocrystallization of hydroxybenzoic acids with hexamine using liquid-assisted grinding shows facile solid state interconversion among different stoichiometric variants. The reversible interconversion caused by varying both the acid and base components in tandem is shown to be a consequence of hydrogen-bonded synthon modularity present in all representative crystal structures. Among a total of 11 complexes, three are salts and eight are cocrystals. The insulated synthons appear as conserved tetrameric motifs in the structures, and the mechanism of interconversion is closely monitored by the synthon modularity. The interconversion is consistent with the theoretically computed stabilization energies of all the tetramers found in this series of cocrystals based on atoms in molecule calculations.

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.

Quantum simulation using fidelity-profile optimization

Experimental quantum simulation of a Hamiltonian H requires unitary operator decomposition (UOD) of its evolution unitary U = exp(-iHt) in terms of native unitary operators of the experimental system. Here, using a genetic algorithm, we numerically evaluate the most generic UOD (valid over a continuous range of Hamiltonian parameters) of the unitary operator U, termed fidelity-profile optimization. The optimization is obtained by systematically evaluating the functional dependence of experimental unitary operators (such as single-qubit rotations and time-evolution unitaries of the system interactions) to the Hamiltonian (H) parameters. Using this technique, we have solved the experimental unitary decomposition of a controlled-phase gate (for any phase value), the evolution unitary of the Heisenberg XY interaction, and simulation of the Dzyaloshinskii-Moriya (DM) interaction in the presence of the Heisenberg XY interaction. Using these decompositions, we studied the entanglement dynamics of a Bell state in the DM interaction and experimentally verified the entanglement preservation procedure of Hou et al. Ann. Phys. (N.Y.) 327, 292 (2012)] in a nuclear magnetic resonance quantum information processor.

C. N. R. Rao and the Growth of Solid State and Materials Chemistry as a Central Domain of Research

In celebrating Professor C. N. R. Rao's 80th birthday, this article recalls his singular contributions to solid state and materials chemistry for about sixty years. In so doing, the article also traces the growth of the field as a central domain of research in chemical sciences from its early origins in Europe. Although Rao's major work lies in solid state and materials chemistry - a field which he started and nurtured in India while its importance was being recognized internationally - his contributions to other areas of chemistry (and physics), viz., molecular spectroscopy, phase transitions, fullerenes, graphene, nanomaterials and multiferroics are equally significant. Illustrative examples of his work devoted to rare earth and transition metal oxides, defects and nonstoichiometry, metal-insulator transitions, investigation of crystal and electronic structures of a variety of solids by means of electron microscopies and photoelectron spectroscopy, superconducting cuprates, magnetoresistive manganites, multiferroic metal oxides of various structures and, last but not the least, development of new strategies for chemical synthesis of a wide variety of solids including nanomaterials and framework solids in different dimensionalities, are highlighted. The article also captures his exemplary role as a science teacher, science educationist and institution builder in post-Independence India.

Dense network of O-H ... O and C-H ... O interactions in the solid state structure of n-pentyl-2-chloro-2-deoxy-alpha-D-manno-sept 3-uloside

Single crystal X-ray structural analysis of a septanoside, namely, n-pentyl-2-chloro-2-deoxy sept-3-uloside (1) provides many finer details of the molecular structure, in addition to its preferred twist-chair conformation, namely, (TC3,4)-T-5,6 conformation. Structural analysis reveals a dense network of O-H...O, C-H...O and van der Waals interactions that stabilize interdigitized, planar bi-layer structure of the crystal lattice. (C) 2014 Elsevier Ltd. All rights reserved.

Phase Evolution in the AuCu/Sn System by Solid-State Reactive Diffusion

The interfacial reactions between several Au(Cu) alloys and pure Sn were studied experimentally at 200A degrees C. Amounts of Cu in the AuSn4 and AuSn2 phases were as low as 1 at.%. On the basis of these experimental results there is no continuous solid solution between (Au,Cu)Sn and (Cu,Au)(6)Sn-5. The copper content of (Au,Cu)Sn was determined to be approximately 7-8 at.%. Substantial amounts of Au were present in the (Cu,Au)(6)Sn-5 and (Cu,Au)(3)Sn phases. Two ternary compounds were formed, one with stoichiometry varying from (Au40.5Cu39)Sn-20.5 to (Au20.2Cu59.3)Sn-20.5 (ternary ``B''), the other with the composition Au34Cu33Sn33 (ternary ``C''). The measured phase boundary compositions of the product phases are plotted on the available Au-Cu-Sn isotherm and the phase equilibria are discussed. The complexity and average thickness of the diffusion zone decreases with increasing Cu content except for the Au(40 at.%Cu) couple.

Real-time magnetic resonance imaging and electromagnetic articulography database for speech production research (TC)

USC-TIMIT is an extensive database of multimodal speech production data, developed to complement existing resources available to the speech research community and with the intention of being continuously refined and augmented. The database currently includes real-time magnetic resonance imaging data from five male and five female speakers of American English. Electromagnetic articulography data have also been presently collected from four of these speakers. The two modalities were recorded in two independent sessions while the subjects produced the same 460 sentence corpus used previously in the MOCHA-TIMIT database. In both cases the audio signal was recorded and synchronized with the articulatory data. The database and companion software are freely available to the research community. (C) 2014 Acoustical Society of America.

Fine-tuning solid-state luminescence in NPIs (1,8-naphthalimides): impact of the molecular environment and cumulative interactions

An investigation of a series of seven angular ``V'' shaped NPIs (1-7) is presented. The effect of substitution of these structurally similar NPIs on their photophysical properties in the solution-state and the solid-state is presented and discussed in light of experimental and computational findings. Compounds 1-7 show negligible to intensely strong emission yields in their solid-state depending on the nature of substituents appended to the oxoaryl moiety. The solution and solid-state properties of the compounds can be directly correlated with their structural rigidity, nature of substituents and intermolecular interactions. The versatile solid-state structures of the NPI siblings are deeply affected by the pendant substituents. All of the NPIs (1-7) show antiparallel dimeric pi-pi stacking interactions in their solid-state which can further extend in a parallel, alternate, orthogonal or lateral fashion depending on the steric and electronic nature of the C-4' substituents. Structural investigations including Hirshfeld surface analysis methods reveal that where strongly interacting systems show weak to moderate emission in their condensed states, weakly interacting systems show strong emission yields under the same conditions. The nature of packing and extended structures also affects the emission colors of the NPIs in their solid-states. Furthermore, DFT computational studies were utilized to understand the molecular and cumulative electronic behaviors of the NPIs. The comprehensive studies provide insight into the condensed-state luminescence of aggregationprone small molecules like NPIs and help to correlate the structure-property relationships.

Reconstruction of Two-Dimensional Spectra from One-Dimensional Projections-Examples from Solid State NMR

The use of Projection Reconstruction (PR) to obtain two-dimensional (2D) spectra from one-dimensional (1D) data in the solid state is illustrated. The method exploits multiple 1D spectra obtained using magic angle spinning and off-magic angle spinning. The spectra recorded under the influence of scaled heteronuclear scalar and dipolar couplings in the presence of homonuclear dipolar decoupling sequences have been used to reconstruct J/D Resolved 2D-NMR spectra. The use of just two 1D spectra is observed sufficient to reconstruct a J-resolved 2D-spectrum while a Separated Local Field (SLF) 2D-NMR spectrum could be obtained from three 1D spectra. The experimental techniques for recording the 10 spectra and procedure of reconstruction are discussed and the reconstructed results are compared with 20 experiments recorded in traditional methods. The application of the technique has been made to a solid polycrystalline sample and to a uniaxially oriented liquid crystal. Implementation of PR-NMR in solid state provides high-resolution spectra as well as leads to significant reduction in experimental time. The experiments are relatively simple and are devoid of several technical complications involved in performing the 2D experiments.