Quantum efficiency and the photonic control of molecular fluorescence in the solid state

We investigate the role of quantum efficiency in determining the extent to which the local photonic environment may alter the spontaneous emission rate of organic dye molecules with broad luminescence spectra. Comparison of theory with experimental results shows that the quantum efficiency is a key determining factor in such control, low quantum efficiencies leading to poor control. These results help establish a firm basis for characterising near-fields in nano-optics and controlling fluorescing species. Received: 31 May 2002 / Revised version: 27 June 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +44-1392/264-111, E-mail: S. Astilean@exeter.ac.uk     

Aspects on Applications of IR Reflectivity- and Raman Scattering-Experiments on Polaritons in Solid State Chemistry and Biophysics

The coupled phonon-photon state called “polariton” is an elementary excitation which exists at all temperatures in single crystalline materials with well defined translational symmetries. In the view of this aspect polaritons turn out to be more important for the dynamics of crystal lattices in general than e.g. magnons or plasmons which normally can be excited only in certain low temperature ranges. The present article summarizes experimental results which all might be applied as analytical methods. An improved method for the determination of fundamental mode frequencies is described. Polariton interactions with localized modes, and second order phonons and the relation to the ferroelectric phase transition mechanism is reviewed. Furthermore experiments concerning parametric light scattering, the TM-reflection technique, the ATR-method, and nonlinear optical experiments are summarized. We finally discuss the question of mechanical-electromagnetic energy conversion and some tentative future aspects.     

Quantum computation with vibrationally excited polyatomic molecules: effects of rotation,level structure,and field gradients

Accurate rotation–vibration energy levels and transition dipoles of the molecule thiophosgene are used to model the execution of quantum gates with shaped laser pulses. Qubits are encoded in 2 ⁿ vibrational computing states on the ground electronic surface of the molecule. Computations are carried out by cycling amplitude between these computing states and a gateway state with a shaped laser pulse. The shaped pulse that performs the computation is represented by a physical model of a 128–1024 channel pulse shaper. Pulse shapes are optimized with a standard genetic algorithm, yielding experimentally realizable computing pulses. The robustness of optimization is studied as a function of the vibrational states selected, rotational level structure, additional vibrational levels not assigned to the computation, and compensation for laser power variation across a molecular ensemble.     

Friction tensor for a pair of Brownian particles: Spurious finite-size effects and molecular dynamics estimates

In this work, we show thatin any finite system, the binary friction tensor for two Brownian particlescannot be directly estimated from an evaluation of the microscopic Green-Kubo formula, involving the time integral of force-force autocorrelation functions. This pitfall is associated with a subtle inversion of the thermodynamic and long-time limits and leads to spurious results for the estimates of the friction matrix based on molecular dynamics simulations. Starting from a careful analysis of the coupled Langevin equations for two interacting Brownian particles, we derive a method to circumvent these effects and extract the binary friction tensor from the correlation function matrix of the instantaneous forces exerted by the bath particles on the fixed Brownian particles, and from the relaxation of the total momentum of the bath in afinite system. The general methodology is applied to the case of two hard or soft Brownian spheres in a bath of light particles. Numerical estimates of the relevant correlation functions and of the resulting self and mutual components of the matrix of friction tensors are obtained by molecular dynamics simulations for various spacings between the Brownian particles. This paper is dedicated to B. Jancovici on the occassion of his 65th birthday.     

Hydrogen, sulphur and chlorine coadsorption on Pd(111): a theoretical study of poisoning and promotion

First principles calculations for the coadsorption of hydrogen with sulphur and chlorine on Pd(111) are presented. Individually, both sulphur and chlorine poison hydrogen adsorption, sulphur being the more efficient poison. The observed sulphur poisoning is a structural effect. The adsorption energy decreases and the diffusion barrier increases for hydrogen atoms in the vicinity of sulphur adatoms. A sulphur coverage of 0.33 ML is sufficient to completely poison hydrogen adsorption on Pd(111). The presence of chlorine adatoms on the sulphur-poisoned surface is found to stabilise localised hydrogen adsorption. The possible promotional effects of chlorine on sulphur-poisoned catalysts are discussed.     

Evaluating the effects of loading parameters on single-crystal slip in tantalum using molecular mechanics

This study is aimed at developing a physics-based crystal plasticity finite element model for body-centred cubic (BCC) metals, through the introduction of atomic-level deformation information from molecular dynamics (MD) investigations of dislocation motion at the onset of plastic flow. In this study, three critical variables governing crystal plasticity mediated by dislocation motion are considered. MD simulations are first performed across a range of finite temperatures up to 600K to quantify the temperature dependence of critical stress required for slip initiation. An important feature of slip in BCC metals is that it is not solely dependent on the Schmid law measure of resolved shear stress, commonly employed in crystal plasticity models. The configuration of a screw dislocation and its subsequent motion is studied under different load orientations to quantify these non-Schmid effects. Finally, the influence of strain rates on thermal activation is studied by inducing higher stresses during activation at higher applied strain rates. Functional dependence of the critical resolved shear stress on temperature, loading orientation and strain rate is determined from the MD simulation results. The functional forms are derived from the thermal activation mechanisms that govern the plastic behaviour and quantification of relevant deformation variables. The resulting physics-based rate-dependent crystal plasticity model is implemented in a crystal plasticity finite element code. Uniaxial simulations reveal orientation-dependent tension–compression asymmetry of yield that more accurately represents single-crystal experimental results than standard models.     

Ethylene, sulphur, and chlorine coadsorption on Pd(111): a theoretical study of poisoning and promotion

First principles calculations for the coadsorption of C₂H₄ with S and Cl on Pd(111) are presented. Sulphur poisons adsorption, decreasing the strength of the ethylene–surface interaction. While low coverages of chlorine alone do not appear to affect ethylene adsorption on the otherwise clean palladium surface, chlorine does act as a promoter on the sulphur poisoned surface, increasing the strength of the ethylene–surface interaction. The promotional effect is attributed to changes in the dative bonding of the molecule and the surface and cannot be explained solely in terms of changes in the metal workfunction.     

Role of oxygen functional groups for structure and dynamics of interfacial water on low rank coal surface: a molecular dynamics simulation

Molecular dynamics simulations were employed to study the effects of oxygen functional groups for structure and dynamics properties of interfacial water molecules on the subbituminous coal surface. Because of complex composition and structure, the graphite surface modified by hydroxyl, carboxyl and carbonyl groups was used to represent the surface model of subbituminous coal according to XPS results, and the composing proportion for hydroxyl, carbonyl and carboxyl is 25:3:5. The hydration energy with ?386.28 kJ/mol means that the adsorption process between water and coal surface is spontaneous. Density profiles for oxygen atoms and hydrogen atoms indicate that the coal surface properties affect the structural and dynamic characteristics of the interfacial water molecules. The interfacial water exhibits much more ordering than bulk water. The results of radial distribution functions, mean square displacement and local self-diffusion coefficient for water molecule related to three oxygen moieties confirmed that the water molecules prefer to absorb with carboxylic groups, and adsorption of water molecules at the hydroxyl and carbonyl is similar.     

Coherent transport in linear arrays of quantum dots: The effects of period doubling and of quasi-periodicity

We evaluate the phase-coherent transport of electrons along linear structures of varying length, which are made from two types of potential wells set in either a periodic or a Fibonacci quasi-periodic sequence. The array is described by a tight-binding Hamiltonian and is reduced to an effective dimer by means of a decimation-renormalization method, extended to allow for connection to external metallic leads, and the transmission coefficient is evaluated in a T-matrix-scattering approach. Parallel behaviors are found for the energy dependence of the density of electron states and of the transmittivity of the array. In particular, we explicitly show that on increasing its length the periodic array undergoes a metal–insulator transition near single occupancy per dot, whereas prominent pseudo-gaps emerge away from the band center in the Fibonacci-ordered array.     

Study of the effects of Cr ions on Yb in Cr,Yb:YAG crystal

The absorption and fluorescence spectra of Cr,Yb:YAG crystal were measured. There are two absorption bands at 940 nm and 968 nm although the absorption coefficient is lower than that of the absorption peak of Yb:YAG superimposed in Cr:YAG absorption peak. The emission peak intensity is 4 times lower than that of Yb:YAG, which may be caused by the existence of the ground state absorption of Cr⁴⁺ which quenches the Yb³⁺ emission intensity. Although the emission peak of Cr,Yb:YAG is lower than that of Yb:YAG, there is an advantage of this crystal which combines the saturable absorber and gain medium into one and can be a self-Q switching laser crystal if Cr,Yb:YAG crystal is pumped with high energy power.     

Rovibrational matrix elements of the multipole moments and of the polarizability of the H2 molecule in the solid phase: Effect of intermolecular potential

Rovibrational matrix elements of the multiple moments Q _l up to rank 10 and of the linear polarizability of the H₂ molecule in the condensed phase have been computed taking into account the effect of the intermolecular potential. Comparison with gas phase matrix elements shows that the effect of solid state interactions is marginal.     

Effects of Poisson's ratio on the band gaps and defect states in two-dimensional vacuum/solid porous phononic crystals

The effects of the Poisson’s ratio of the solid host on the band gaps and point defect states of the mixed elastic wave modes in two-dimensional vacuum/solid porous PNCs are studied by numerical simulations. Four typical systems are considered. The four systems are, respectively, (I) the system with a square lattice and circular pores, (II) the system with a hexagonal lattice and circular pores, (III) the system with a square lattice and square pores and (IV) the system with a hexagonal lattice and regular-hexagonal pores. In the latter two systems, with respect to the outer boundaries of the Wigner-Seitz unit cell, the pores rotate 45° and 30°, respectively. Some observable effects of the Poisson’s ratio are found in the numerical results. Especially, the variations of the band gap boundaries with the Poisson’s ratio exhibit relatively consistent behaviors. With the increase of the Poisson’s ratio, the normalized frequency of a band gap boundary generally increases, except that in system (III) the normalized frequency of the upper boundary of the first band gap remains almost unchanged. Detailed interpretations on this phenomenon are given.     

Control of amplification without inversion in H2 and LiH molecules: Dependence on relative magnitude of probe and coherent field Rabi frequencies in three-level Λ system

Dependence of amplification without inversion (AWI) on the relative strength of probe and coherent field Rabi frequencies has been studied in H₂ and LiH molecules for three-level Λ configuration. We have derived exact analytical expressions for coherences and populations keeping all the orders of probe field Rabi frequency (G) and coherent field Rabi frequency. (Θ) in the steady state limit. Previously, first-order approximation (i.e. keeping only the first-order term in G) was used and hence AWI was studied for the condition Θ>>G. Here, by using the exact analytical expressions of coherences and populations, we have shown that AWI is maximum when Θ is within the same order of probe field Rabi frequency G irrespective of the choice of different ro-vibrational transitions in both the molecules. However, the shape of the gain profile and the maximum value of gain on the probe field and the absorption on coherent field depend on the choice of different ro-vibrational levels as the upper lasing levels. Effect of bidirectional pumping, homogeneous and inhomogeneous broadening on AWI process has been studied. By solving the density matrix equations numerically it has been shown that both the transient and the steady state AWI can be obtained and the numerical values of coherences and populations at large time are in very good agreement with exact analytical values in the steady state limit. It has been shown that in molecules AWI can be obtained on probe field of smaller wavelength than that of the coherent field which has not been observed in atoms so far.     

Pressure effects on diffusion in liquid ammonia : A simulation study using a combination of isobaric-isothermal and microcanonical molecular dynamics

The effects of pressure on translational and rotational diffusion in liquid ammonia are investigated by means of molecular dynamics simulations. Calculations are done at two different temperatures and at many different pressures by using a two-part protocol involving molecular dynamics in isobaric-isothermal ensemble in the first part and in microcanonical ensemble in the second part. Our results are analyzed in terms of pressure-induced changes in structural properties such as packing and hydrogen bond properties. Also, the present results of liquid ammonia are compared with corresponding results for other hydrogen bonded liquids that were reported in recent years.      

The effects of indium segregation on exciton binding energy and oscillator strength in GaInAs/GaAs quantum wells

We solve analytically the Schrödinger equation taking into account the shape changes of GaInAs/GaAs quantum wells due to indium segregation during the MBE growth by using transfer matrix method. The indium compositional profiles of the quantum wells are provided using the phenomenological model. The fundamental transition energy, binding energy and oscillator strength of excitons as a function of indium segregation coefficient R$R$ and well width are studied. For narrow wells (less than 40 ML), the exciton binding energy and oscillator strength decrease, but for wide wells (larger than 40 ML), increase with increasing the segregation coefficient R$R$. It is shown that indium segregation degrades the optical properties and results in a blue-shift of exciton transition energy in GaInAs/GaAs quantum wells.     

Self-assembled monolayer of o-aminothiophenol on Fe(1 1 0) surface: a combined study by electrochemistry, in situ STM, and molecular simulations

Electrochemical measurements, in situ scanning tunneling microscopy (STM) observation, and molecular mechanics (MM) simulations were performed to study the physiochemical properties such as the corrosion-inhibition effect and the optimal packing structure of o-aminothiophenol (OATP) self-assembled monolayer (SAM) formed on Fe(1 1 0) surface in 0.1 M NaClO₄ solution. The formation of OATP SAMs drastically depressed the Faradaic processes at the Fe(1 1 0) surface and reduced the electrical double-layer capacitance at the electrode/electrolyte interface, revealing the anticorrosion property and the blocking behavior of OATP adlayers. Two-dimensional ordered molecular arrays of OATP on Fe(1 1 0) surface with a p(2 × 2) commensurate structure were observed by STM measurements. MM calculations showed that the p(2 × 2) packing pattern is indeed the preferable structure for OATP molecules adsorbed on Fe(1 1 0), in accordance with STM experiments. The OATP SAM on Fe(1 1 0) is ≈0.50 nm in thickness and with a dielectric constant of ∼7.0.     

Anchoring group effects in molecular devices: An ab initio study on the electronic transport of a carbon-dimer

The conductance of a molecular device is sensitive to the contact geometry between the molecules and the probing electrodes. Taking a carbon-dimer C₂ as an example and connecting it to the electrodes by different linking atoms H, Cu and S, we investigate the anchoring group effect in molecular devices by the first-principles approaches. The results exhibit that, depending on the anchoring groups and the subsequent different metal-molecule chemical bonds, the current varies over more than two orders of magnitude under the same bias. This emphasizes the great importance of the anchoring groups in molecular devices.     

Low temperature specific heat of molecular rings: a study on the effects of the internal guest substitution and on the lattice contribution

The effects of the internal guest substitution within hexa-iron molecular rings (Na:Fe6 and Li:Fe6) have been investigated by means of low temperature specific heat (LTSH) measurements. By changing Na to Li as central metal ion, the Schottky anomaly shifts towards lower temperatures. The data analysis is supported by the study of the LTSH of the non-magnetic Na:Ga6 compound which has the same core structure as the iron rings. For the non-magnetic Na:Ga6, significant deviations from the simple Debye law were found and the use of conventional C vs. T fitting curves is critically discussed. The singlet-triplet energy gap ( K) and its zero-field splitting ( K) evaluated from the magnetic contribution of the Li:Fe6 LTSH are compared to values estimated by high field torque magnetometry. Received 25 November 1999