Hydrogen bonding and collective proton modes in clusters and periodic layers of squaric acid: A density functional study

Hydrogen bonding in clusters and extended layers of squaric acid molecules has been investigated by density functional computations. Equilibrium geometries, harmonic vibrational frequencies, and energy barriers for proton transfer along hydrogen bonds have been determined using the Car-Parrinello method. The results provide crucial parameters for a first principles modeling of the potential energy surface, and highlight the role of collective modes in the low-energy proton dynamics. The importance of quantum effects in condensed squaric acid systems has been investigated, and shown to be negligible for the lowest-energy collective proton modes. This information provides a quantitative basis for improved atomistic models of the order-disorder and displacive transitions undergone by squaric acid crystals as a function of temperature and pressure. (C) 2001 American Institute of Physics.

Nonlinear excitations in strongly-coupled plasma lattices: envelope solitons, kinks and intrinsic localized modes

Ensembles of charged particles (plasmas) are a highly complex form of matter, most often modeled as a many-body system characterized by weak inter-particle interactions (electrostatic coupling). However, strongly-coupled plasma configurations have recently been produced in laboratory, either by creating ultra-cold plasmas confined in a trap or by manipulating dusty plasmas in discharge experiments. In this paper, the nonlinear aspects involved in the motion of charged dust grains in a one-dimensional plasma monolayer (crystal) are discussed. Different types of collective excitations are reviewed, and characteristics and conditions for their occurrence in dusty plasma crystals are discussed, in a quasi-continuum approximation. Dust crystals are shown to support nonlinear kink-shaped supersonic solitary longitudinal excitations, as well as modulated envelope localized modes associated with longitudinal and transverse vibrations. Furthermore, the possibility for intrinsic localized modes (ILMs) — Discrete Breathers (DBs) — to occur is investigated, from first principles. The effect of mode-coupling is also briefly considered. The relation to previous results on atomic chains, and also to experimental results on strongly-coupled dust layers in gas discharge plasmas, is briefly discussed.

Collective excitations of trapped Bose-Einstein condensates in the energy and time domains

A time-dependent method for calculating the collective excitation frequencies and densities of a trapped, inhomogeneous Bose-Einstein condensate with circulation is presented. The results are compared with time-independent solutions of the Bogoliubov-de Gennes equations. The method is based on time-dependent linear-response theory combined with spectral analysis of moments of the excitation modes of interest. The technique is straightforward to apply, extremely efficient in our implementation with parallel fast Fourier transform methods, and produces highly accurate results. For high dimensionality or low symmetry the time-dependent approach is a more practical computational scheme and produces accurate and reliable data. The method is suitable for general trap geometries, condensate flows and condensates permeated with defects and vortex structures.

Developing Creative Solutions to the Problems of Children and their Families: Communicative Reason and the use fo Forum Theatre

Building on Habermas’s conceptualisation of modes of reasoning, the authors proposed that an application of critical theory to the present bureaucratised nature of communication between state representatives and welfare recipients (Howe 1992) might open up ways in which social workers could reconceptualise their practice. In a subsequent edition of this journal, three of the present authors introduced the radical theatre of Augusto Boal as a methodology which might provide an expressive route for social workers seeking to build a practice combining the intellectual analysis of critical theory with new ways of working (Spratt et al. 2000). Boal’s method recognises the oppressed status of groups who come to the attention of agents of the state and, through the use of a range of theatrical techniques, introduces strategies to facilitate the conscious recognition of such collective oppressions and develop dialogical ways to address them. In the last paper, the authors presented one such technique, ‘image theatre’, and demonstrated its use with social workers in consciousness raising and developing strategies for collective action.

Entanglement between collective operators in a linear harmonic chain

We investigate entanglement between collective operators of two blocks of oscillators in an infinite linear harmonic chain. These operators are defined as averages over local operators (individual oscillators) in the blocks. On the one hand, this approach of "physical blocks" meets realistic experimental conditions, where measurement apparatuses do not interact with single oscillators but rather with a whole bunch of them, i.e., where in contrast to usually studied "mathematical blocks" not every possible measurement is allowed. On the other, this formalism naturally allows the generalization to blocks which may consist of several noncontiguous regions. We quantify entanglement between the collective operators by a measure based on the Peres-Horodecki criterion and show how it can be extracted and transferred to two qubits. Entanglement between two blocks is found even in the case where none of the oscillators from one block is entangled with an oscillator from the other, showing genuine bipartite entanglement between collective operators. Allowing the blocks to consist of a periodic sequence of subblocks, we verify that entanglement scales at most with the total boundary region. We also apply the approach of collective operators to scalar quantum field theory.

Electron-phonon interaction in atomic-scale conductors: Einstein oscillators versus full phonon modes

Two extreme pictures of electron-phonon interactions in nanoscale conductors are compared: one in which the vibrations are treated as independent Einstein atomic oscillators, and one in which electrons are allowed to couple to the full, extended phonon modes of the conductor. It is shown that, under a broad range of conditions, the full-mode picture and the Einstein picture produce essentially the same net power at any given atom in the nanojunction. The two pictures begin to differ significantly in the limit of low lattice temperature and low applied voltages, where electron-phonon scattering is controlled by the detailed phonon energy spectrum. As an illustration of the behaviour in this limit, we study the competition between trapped vibrational modes and extended modes in shaping the inelastic current-voltage characteristics of one-dimensional atomic wires.

Superfluid toroidal currents in atomic condensates

The spectrum of collective excitations of oblate toroidal condensates within the Bogoliubov approximation was studied, and the dynamical stability of ring currents around the torus explored. The transition from spheroidal to toroidal geometry of the trap displaced the energy levels into narrow bands. A simple, but accurate, formula was detailed for the lowest angular acoustic modes of excitation, and the splitting energy when a background current is present.

Softened C-H modes of adsorbed methyl and their implications for dehydrogenation: An ab initio study

To investigate the softening of CH vibrational frequencies and their implications for dehydrogenation of adsorbed hydrocarbons, an issue of scientific and technological importance, density functional theory calculations have been performed on the chemisorption and dehydrogenation of CH3 on Cu(111) and Pt(111) surfaces. By comparing these results with those of Ni(111) we find that the CH bonds of the adsorbate, when close enough, interact with metal atoms of the surface. It is this interaction and its associated lengthening and weakening of CH bonds that is the physical origin of mode softening. We rule out the possibility of a relationship between the mere presence of mode softening and dehydrogenation. We do show, however, that there is a clear relationship between the extent to which a surface can induce mode softening and the activation energy to dehydrogenation. In addition, periodic trends concerning the extent of mode softening are reproduced. (C) 2001 American Institute of Physics.

Resonance Raman and DFT studies of tetra-tert-butyl porphine: Assignment of strongly enhanced distortion modes in a ruffled porphyrin

The free-base form of tetra-tert-butyl porphine (TtBP), which has extremely bulky meso substituents, is severely distorted from planarity, with a ruffling angle of 65.5degrees. The resonance Raman spectrum of TtBP (lambda(ex) = 457.9 nm) and its d(2), d(8), and d(10) isotopomers have been recorded, and while the spectra show high-frequency bands similar to those observed for planar meso-substituted porphyrins, there are several additional intense bands in the low-frequency region. Density functional calculations at the B3-LYP/6-31G(d) level were carried out for all four isotopomers, and calculated frequencies were scaled using a single factor of 0.98. The single factor scaling approach was validated on free base porphine where the RMS error was found to be 14.9 cm(-1). All the assigned bands in the high-frequency (> 1000 cm(-1)) region of TtBP were found to be due to vibrations similar in character to the in-plane skeletal modes of conventional planar porphyrins. In the low-frequency region, two of the bands, assigned as nu(8) (ca. 330 cm(-1)) and nu(16) (ca. 540 cm(-1)), are also found in planar porphyrins such as tetra-phenyl porphine (TPP) and tetra-iso-propyl porphine (IPP). Of the remaining three very strong bands, the lowest frequency band was assigned as gamma(12) (pyr swivel, obsd 415 cm(-1), calcd 407 cm(-1) in do). The next band, observed at 589 cm-1 in the do compound (calcd 583 cm(-1)), was assigned as a mode whose composition is a mixture of modes that were previously labeled gamma(13) (gamma(CmCaHmCa)) andy gamma(11) (pyr fold(asym)) in NiOEP. The final strong band, observed at 744 cm(-1) (calcd 746 cm(-1)), was assigned to a mode whose composition is again a mixture of gamma(11) and gamma(13), although here it is gamma(11) rather than gamma(13) which predominates. These bands have characters and positions similar to those of three of the four porphyrin ring-based, weak bands that have previously been observed for NiTPP. In addition there are several weaker bands in the TtBP spectra that are also