Harmonic qualities in Debussy's "Les sons et les parfums tournent dans l'air du soir"

This analysis of the fourth piece from Debussy's Préludes Book I illustrates typical harmonic techniques of Debussy as manipulations of harmonic qualities. We quantify harmonic qualities via the magnitudes and squared-magnitudes of the coefficients of the discrete Fourier transform (DFT) of pitch class sets, following Ian Quinn. The principal activity of the piece occurs in the fourth and fifth coefficients, the octatonic and diatonic qualities, respectively. The development of harmonic ideas can therefore be mapped out in a two-dimensional octatonic/diatonic phase space. Whole-tone material, representative of the sixth coefficient of the DFT, also plays an important role. I discuss Debussy's motivic work, how features of tonality – diatonicity and harmonic function – relate to his musical language, and the significance of perfectly balanced set classes, which are a special case of nil DFT coefficients.Accepted manuscrip

Structure and electronic properties of transition-metal/Mg bimetallic clusters at realistic temperatures and oxygen partial pressures

Composition, atomic structure, and electronic properties of TM$_x$Mg$_y$O$_z$ clusters (TM = Cr, Ni, Fe, Co, $x+y \leq 3$) at realistic temperature $T$ and partial oxygen pressure $p_{\textrm{O}_2}$ conditions are explored using the {\em ab initio} atomistic thermodynamics approach. The low-energy isomers of the different clusters are identified using a massively parallel cascade genetic algorithm at the hybrid density-functional level of theory. On analyzing a large set of data, we find that the fundamental gap E$_\textrm{g}$ of the thermodynamically stable clusters are strongly affected by the presence of Mg-coordinated O$_2$ moieties. In contrast, the nature of the transition metal does not play a significant role in determining E$_\textrm{g}$. Using E$_\textrm{g}$ of a cluster as a descriptor of its redox properties, our finding is against the conventional belief that the transition metal plays the key role in determining the electronic and therefore chemical properties of the clusters. High reactivity may be correlated more strongly with oxygen content in the cluster than with any specific TM type.Comment: 7 pages, 5 figure

Equations of state and stability of MgSiO3_3 perovskite and post-perovskite phases from quantum Monte Carlo simulations

We have performed quantum Monte Carlo (QMC) simulations and density functional theory (DFT) calculations to study the equations of state of MgSiO$_3$ perovskite (Pv) and post-perovskite (PPv), up to the pressure and temperature conditions of the base of Earth's lower mantle. The ground state energies were derived using QMC and the temperature dependent Helmholtz free energies were calculated within the quasi-harmonic approximation and density functional perturbation theory. The equations of state for both phases of MgSiO$_3$ agree well with experiments, and better than those from generalized gradient approximation (GGA) calculations. The Pv-PPv phase boundary calculated from our QMC equations of states is also consistent with experiments, and better than previous LDA calculations. We discuss the implications for double crossing of the Pv-PPv boundary in the Earth

Electronic Structure Shift of Deep Nanoscale Silicon by SiO2_2- vs. Si3_3N4_4-Embedding as Alternative to Impurity Doping

Conventional impurity doping of deep nanoscale silicon (dns-Si) used in ultra large scale integration (ULSI) faces serious challenges below the 14 nm technology node. We report on a new fundamental effect in theory and experiment, namely the electronic structure of dns-Si experiencing energy offsets of ca. 1 eV as a function of SiO$_2$- vs. Si$_3$N$_4$-embedding with a few monolayers (MLs). An interface charge transfer (ICT) from dns-Si specific to the anion type of the dielectric is at the core of this effect and arguably nested in quantum-chemical properties of oxygen (O) and nitrogen (N) vs. Si. We investigate the size up to which this energy offset defines the electronic structure of dns-Si by density functional theory (DFT), considering interface orientation, embedding layer thickness, and approximants featuring two Si nanocrystals (NCs); one embedded in SiO$_2$ and the other in Si$_3$N$_4$. Working with synchrotron ultraviolet photoelectron spectroscopy (UPS), we use SiO$_2$- vs. Si$_3$N$_4$-embedded Si nanowells (NWells) to obtain their energy of the top valence band states. These results confirm our theoretical findings and gauge an analytic model for projecting maximum dns-Si sizes for NCs, nanowires (NWires) and NWells where the energy offset reaches full scale, yielding to a clear preference for electrons or holes as majority carriers in dns-Si. Our findings can replace impurity doping for n/p-type dns-Si as used in ultra-low power electronics and ULSI, eliminating dopant-related issues such as inelastic carrier scattering, thermal ionization, clustering, out-diffusion and defect generation. As far as majority carrier preference is concerned, the elimination of those issues effectively shifts the lower size limit of Si-based ULSI devices to the crystalization limit of Si of ca. 1.5 nm and enables them to work also under cryogenic conditions.Comment: 14 pages, 17 Figures with a total 44 graph

High-pressure phase and transition phenomena in ammonia borane NH3BH3 from X-ray diffraction, Landau theory, and ab initio calculations

Structural evolution of a prospective hydrogen storage material, ammonia borane NH3BH3, has been studied at high pressures up to 12 GPa and at low temperatures by synchrotron powder diffraction. At 293 K and above 1.1 GPa a disordered I4mm structure reversibly transforms into a new ordered phase. Its Cmc21 structure was solved from the diffraction data, the positions of N and B atoms and the orientation of NH3 and BH3 groups were finally assigned with the help of density functional theory calculations. Group-theoretical analysis identifies a single two-component order parameter, combining ordering and atomic displacement mechanisms, which link an orientationally disordered parent phase I4mm with ordered distorted Cmc21, Pmn21 and P21 structures. We propose a generic phase diagram for NH3BH3, mapping three experimentally found and one predicted (P21) phases as a function of temperature and pressure, along with the evolution of the corresponding structural distortions. Ammonia borane belongs to the class of improper ferroelastics and we show that both temperature- and pressure-induced phase transitions can be driven to be of the second order. The role of N-H...H-B dihydrogen bonds and other intermolecular interactions in the stability of NH3BH3 polymorphs is examined.Comment: 23 pages, 7 figure