Coupling Methylammonium and Formamidinium Cations With Halide Anions: Hybrid Orbitals, Hydrogen Bonding, and the Role of Dynamics

The electronic structures of four precursors for organic-inorganic hybrid perovskites, namely, methylammonium chloride and iodide, as well as formamidinium bromide and iodide, are investigated by X-ray emission (XE) spectroscopy at the carbon and nitrogen K-edges. The XE spectra are analyzed based on density functional theory calculations. We simulate the XE spectra at the Kohn-Sham level for ground-state geometries and carry out detailed analyses of the molecular orbitals and the electronic density of states to give a thorough understanding of the spectra. Major parts of the spectra can be described by the model of the corresponding isolated organic cation, whereas high-emission energy peaks in the nitrogen K-edge XE spectra arise from electronic transitions involving hybrids of the molecular and atomic orbitals of the cations and halides, respectively. We find that the interaction of the methylammonium cation is stronger with the chlorine than with the iodine anion. Furthermore, our detailed theoretical analysis highlights the strong influence of ultrafast proton dynamics in the core-excited states, which is an intrinsic effect of the XE process. The inclusion of this effect is necessary for an accurate description of the experimental nitrogen K-edge X-ray emission spectra and gives information on the hydrogen-bonding strengths in the different precursor materials

Electronic structure effects in liquid water studied by photoelectron spectroscopy and density functional theory

We present valence photoelectron emission spectra of liquid water in comparison with gas-phase water, ice close to the melting point, low temperature amorphous and crystalline ice. All aggregation states have major electronic structure changes relative to the free molecule, with rehybridization and development of bonding and anti-bonding states accompanying the hydrogen bond formation. Sensitivity to the local structural order, most prominent in the shape and splitting of the occupied 3a{sub 1} orbital, is understood from the electronic structure averaging over various geometrical structures, and reflects the local nature of the orbital interaction

A factor analysis of the SSQ (Speech, Spatial, and Qualities of Hearing Scale)

OBJECTIVE: The speech, spatial, and qualities of hearing questionnaire (SSQ) is a self-report test of auditory disability. The 49 items ask how well a listener would do in many complex listening situations illustrative of real life. The scores on the items are often combined into the three main sections or into 10 pragmatic subscales. We report here a factor analysis of the SSQ that we conducted to further investigate its statistical properties and to determine its structure. DESIGN: Statistical factor analysis of questionnaire data, using parallel analysis to determine the number of factors to retain, oblique rotation of factors, and a bootstrap method to estimate the confidence intervals. STUDY SAMPLE: 1220 people who have attended MRC IHR over the last decade. RESULTS: We found three clear factors, essentially corresponding to the three main sections of the SSQ. They are termed "speech understanding", "spatial perception", and "clarity, separation, and identification". Thirty-five of the SSQ questions were included in the three factors. There was partial evidence for a fourth factor, "effort and concentration", representing two more questions. CONCLUSIONS: These results aid in the interpretation and application of the SSQ and indicate potential methods for generating average scores

Hydration dynamics gives the distinctive brown color in the "brown ring" nitrate test

The chemistry of the brown-ring test has been investigated for nearly a century. Though recent studies have focused on solid state structure determination and the measurement of spectra, mechanistic details and kinetics, the aspects of solution structure and dynamics remain unknown. From ab initio molecular dynamics simulations of the brown-ring complex in aqueous solution, we have identified that the classically established pseudo-octahedral [Fe(H2O)5(NO)]2+ complex is in equilibrium with a square-pyramidal [Fe(H2O)4(NO)]2+ complex through the exchange of one of the coordinated H2O molecules. We also find, using ab-initio multi-reference methods, that the mixture of these two complexes is what gives the distinctive brown coloration to the brown-ring test. We show that its UV-vis spectrum can be theoretically reproduced only by accounting these two species and not the [Fe(H2O)5(NO)]2+ complex alone. The energetics of the two complexes are also investigated with multi-reference methods