Pore confinement effects and stabilization of carbon nitride oligomers in macroporous silica for photocatalytic hydrogen production

An ordered macroporous host (mac-SiO2) has been used to prevent aggregation of layered photocatalysts based on carbon nitride. Using typical carbon nitride synthesis conditions, cyanamide was condensed at 550 °C in the presence and absence of mac-SiO2. Condensation in the absence of mac-SiO2 results in materials with structural characteristics consistent with the carbon nitride, melon, accompanied by ca. 2 wt% carbonization. For mac-SiO2 supported materials, condensation occurs with greater carbonization (ca. 6 wt%). On addition of 3 wt% Pt cocatalyst photocatalytic hydrogen production under visible light is found to be up to 10 times greater for the supported composites. Time-resolved photoluminescence spectroscopy shows that excited state relaxation is more rapid for the mac-SiO2 supported materials suggesting faster electron-hole recombination and that supported carbon nitride does not exhibit improved charge separation. CO2 temperature programmed desorption indicates that enhanced photoactivity of supported carbon nitride is attributable to an increased surface area compared to bulk carbon nitride and an increase in the concentration of weakly basic catalytic sites, consistent with carbon nitride oligomers.

Dynamical interplay between ground and excited states in quantum dot laser

Full text: Semiconductor quantum dot lasers are attractive for multipletechnological applications in biophotonics. Simultaneous two-state lasing ofground state (GS) and excited state (ES) electrons and holes in QD lasers ispossible under a certain parameter range. It has already been investigated in steady-stateoperations and in dynamical regimes and is currently a subject of the intesiveresearch. It has been shown that the relaxation frequency in the two-state lasingregime is not a function of the total intensity [1], as could be traditionallyexpected.In this work we study damping relaxation oscillations in QD lasersimultaneously operating at two transitions, and find that under variouspumping conditions, the frequency of oscillations may decrease, increase orstay without change in time as shown in Fig1.The studied QD laser structure wasgrown on a GaAs substrate by molecular-beam epitaxy. The active region includedfive layers of self-assembled InAs QDs separated with a GaAs spacer from a5.3nm thick covering layer of InGaAs and processed into 4mm-wide mesa stripe devices. The 2.5mm long lasers withhigh-and antireflection coatings on the rear and front facets lasesimultaneously at the GS (around 1265nm) and ES (around 1190nm) in the wholerange of pumping. Pulsed electrical pumping obtained from a high power (up to2A current) pulse source was used to achieve high output power operation. We simultaneously detect the total output and merely ES output using aBragg filter transmitting the short-wavelength and reflecting the long-wavelengthradiation. Typical QD does not demonstrate relaxation oscillations frequencybecause of the strong damping [2]. It is confirmed for the low (I<0.68A) andhigh (I>1.2 A) range of the pump currents in our experiments. The situationis different for a short range of the medium currents (0.68Arelaxation oscillations to non-instantaneousturn on of the pumping source which activates with 5ns rise time and discussthe swap of the oscillation's frequency in time to spectral shifts caused by thermaleffects. [1] M.Abusaa, J. Danckaert, E. A. Viktorov, and T. Erneux, Phys. Rev. A 87, 063827(2013). [2] T.Erneux, E. A. Viktorov, and P. Mandel, Phys. Rev. A 76,023819 (2007). 1 © 2014 IEEE.

Dropout dynamics in pulsed quantum dot lasers due to mode jumping

We examine the response of a pulse pumped quantum dot laser both experimentally and numerically. As the maximum of the pump pulse comes closer to the excited-state threshold, the output pulse shape becomes unstable and leads to dropouts. We conjecture that these instabilities result from an increase of the linewidth enhancement factor α as the pump parameter comes close to the excitated state threshold. In order to analyze the dynamical mechanism of the dropout, we consider two cases for which the laser exhibits either a jump to a different single mode or a jump to fast intensity oscillations. The origin of these two instabilities is clarified by a combined analytical and numerical bifurcation diagram of the steady state intensity modes.

The effect of slow passage in the pulse-pumped quantum dot laser

In recent years, quantum-dot (QD) semiconductor lasers attract significant interest in many practical applications due to their advantages such as high-power pulse generation because to the high gain efficiency. In this work, the pulse shape of an electrically pumped QD-laser under high current is analyzed. We find that the slow rise time of the pulsed pump may significantly affect the high intensity output pulse. It results in sharp power dropouts and deformation of the pulse profile. We address the effect to dynamical change of the phase-amplitude coupling in the proximity of the excited state (ES) threshold. Under 30ns pulse pumping, the output pulse shape strongly depends on pumping amplitude. At lower currents, which correspond to lasing in the ground state (GS), the pulse shape mimics that of the pump pulse. However, at higher currents the pulse shape becomes progressively unstable. The instability is greatest when in proximity to the secondary threshold which corresponds to the beginning of the ES lasing. After the slow rise stage, the output power sharply drops out. It is followed by a long-time power-off stage and large-scale amplitude fluctuations. We explain these observations by the dynamical change of the alpha-factor in the QD-laser and reveal the role of the slowly rising pumping processes in the pulse shaping and power dropouts at higher currents. The modeling is in very good agreement with the experimental observations. © 2014 SPIE.

Numerical modeling of holmium-doped fluoride fiber lasers

We combine all the known experimental demonstrations and spectroscopic parameters into a numerical model of the Ho3+ -doped fluoride glass fiber laser system. Core-pumped and cladding-pumped arrangements were simulated for all the population-bottlenecking mitigation schemes that have been tested, and good agreement between the model and the previously reported experimental results was achieved in most but not in all cases. In a similar way to Er3+ -doped fluoride glass fiber lasers, we found that the best match with measurements required scaled-down rate parameters for the energy transfer processes that operate in moderate to highly concentrated systems. The model isolated the dominant processes affecting the performance of each of the bottlenecking mitigation schemes and pump arrangements. It was established that pump excited-state absorption is the main factor affecting the performance of the core-pumped demonstrations of the laser, while energy transfer between rare earth ions is the main factor controlling the performance in cladding-pumped systems.

Fast and slowly evolving vector solitons in mode-locked fibre lasers

We report on a new vector model of an erbium-doped fibre laser mode locked with carbon nanotubes. This model goes beyond the limitations of the previously used models based on either coupled nonlinear Schrödinger or Ginzburg-Landau equations. Unlike the previous models, it accounts for the vector nature of the interaction between an optical field and an erbium-doped active medium, slow relaxation dynamics of erbium ions, linear birefringence in a fibre, linear and circular birefringence of a laser cavity caused by in-cavity polarization controller and light-induced anisotropy caused by elliptically polarized pump field. Interplay of aforementioned factors changes coherent coupling of two polarization modes at a long time scale and so results in a new family of vector solitons (VSs) with fast and slowly evolving states of polarization. The observed VSs can be of interest in secure communications, trapping and manipulation of atoms and nanoparticles, control of magnetization in data storage devices and many other areas.

Slow passage through thresholds in quantum dot lasers

A turn on of a quantum dot (QD) semiconductor laser simultaneously operating at the ground state (GS) and excited state (ES) is investigated both experimentally and theoretically. We find experimentally that the slow passage through the two successive laser thresholds may lead to significant delays in the GS and ES turn ons. The difference between the turn-on times is measured as a function of the pump rate of change and reveals no clear power law. This has motivated a detailed analysis of rate equations appropriate for two-state lasing QD lasers. We find that the effective time of the GS turn on follows an -1/2 power law provided that the rate of change is not too small. The effective time of the ES transition follows an -1 power law, but its first order correction in ln is numerically significant. The two turn ons result from different physical mechanisms. The delay of the GS transition strongly depends on the slow growth of the dot population, whereas the ES transition only depends on the time needed to leave a repellent steady state.

Impact of the carrier relaxation paths on two-state operation in quantum dot lasers

We study InGaAs QD laser operating simultaneously at ground (GS) and excited (ES) states under 30ns pulsed-pumping and distinguish three regimes of operation depending on the pump current and the carrier relaxation pathways. An increased current leads to an increase in ES intensity and to a decrease in GS intensity (or saturation) for low pump range, as typical for the cascade-like pathway. Both the GS and ES intensities are steadily increased for high current ranges, which prove the dominance of the direct capture pathway. The relaxation oscillations are not pronounced for these ranges. For the mediate currents, the interplay between the both pathways leads to the damped large amplitude relaxation oscillations with significant deviation of the relaxation oscillation frequency from the initial value during the pulse.

Imaging the dynamics of the auditory steady-state evoked response

This study used magnetoencephalography (MEG) to examine the dynamic patterns of neural activity underlying the auditory steady-state response. We examined the continuous time-series of responses to a 32-Hz amplitude modulation. Fluctuations in the amplitude of the evoked response were found to be mediated by non-linear interactions with oscillatory processes both at the same source, in the alpha and beta frequency bands, and in the opposite hemisphere. © 2005 Elsevier Ireland Ltd. All rights reserved.

Controlling protein molecular dynamics:how to accelerate folding while preserving the native state

The dynamics of peptides and proteins generated by classical molecular dynamics (MD) is described by using a Markov model. The model is built by clustering the trajectory into conformational states and estimating transition probabilities between the states. Assuming that it is possible to influence the dynamics of the system by varying simulation parameters, we show how to use the Markov model to determine the parameter values that preserve the folded state of the protein and at the same time, reduce the folding time in the simulation. We investigate this by applying the method to two systems. The first system is an imaginary peptide described by given transition probabilities with a total folding time of 1 micros. We find that only small changes in the transition probabilities are needed to accelerate (or decelerate) the folding. This implies that folding times for slowly folding peptides and proteins calculated using MD cannot be meaningfully compared to experimental results. The second system is a four residue peptide valine-proline-alanine-leucine in water. We control the dynamics of the transitions by varying the temperature and the atom masses. The simulation results show that it is possible to find the combinations of parameter values that accelerate the dynamics and at the same time preserve the native state of the peptide. A method for accelerating larger systems without performing simulations for the whole folding process is outlined.

T-cell epitope prediction and immune complex simulation using molecular dynamics:state of the art and persisting challenges

Atomistic Molecular Dynamics provides powerful and flexible tools for the prediction and analysis of molecular and macromolecular systems. Specifically, it provides a means by which we can measure theoretically that which cannot be measured experimentally: the dynamic time-evolution of complex systems comprising atoms and molecules. It is particularly suitable for the simulation and analysis of the otherwise inaccessible details of MHC-peptide interaction and, on a larger scale, the simulation of the immune synapse. Progress has been relatively tentative yet the emergence of truly high-performance computing and the development of coarse-grained simulation now offers us the hope of accurately predicting thermodynamic parameters and of simulating not merely a handful of proteins but larger, longer simulations comprising thousands of protein molecules and the cellular scale structures they form. We exemplify this within the context of immunoinformatics.

Molecular dynamics study of solvent transport in nanoscale osmosis

An ideal of osmotic equilibrium between an ideal solution and pure solvent separated by a semi-permeable membrane is studied numerically using the method of molecular dynamics. The osmotic flow is observed as the inflow of the solvent across the membrane from the dilute to the concentrated side. The validity of van't Hoff's law for osmotic pressure is confirmed over a wide range of concentrations. It is found that the law is established by a balance between non-uniform partial pressures of solute and solvent. Furthermore, the present model permits an understanding of the mechanism of the osmotic flow in the relaxation process as the liquids evolve from the initial state to the equilibrium state. We focus in particular on the interaction between solute and solvent. ©2008 The Physical Society of Japan.

Real and imaginary parts of the vibrational relaxation of acetonitrile in its electrolyte solutions:new results for the dynamics of solvent molecules

Isotropic scattering Raman spectra of liquid acetonitrile (AN) solutions of LiBF4 and NaI at various temperatures and concentrations have been investigated. For the first time imaginary as well as real parts of the solvent vibrational correlation functions have been extracted from the spectra. Such imaginary parts are currently an important component of modern theories of vibrational relaxation in liquids. This investigation thus provides the first experimental data on imaginary parts of a correlation function in AN solutions. Using the fitting algorithm we recently developed, statistically confident models for the Raman spectra were deduced. The parameters of the band shapes, with an additional correction, of the ν2 AN vibration (CN stretching), together with their confidence intervals are also reported for the first time. It is shown that three distinct species, with lifetimes greater than ∼10−13 s, of the AN molecules can be detected in solutions containing Li+ and Na+. These species are attributed to AN molecules directly solvating cations; the single oriented and polarised molecules interleaving the cation and anion of a Solvent Shared Ion Pair (SShIP); and molecules solvating anions. These last are considered to be equivalent to the next layer of solvent molecules, because the CN end of the molecule is distant from the anion and thus less affected by the ionic charge compared with the anion situation. Calculations showed that at the concentrations employed, 1 and 0.3 M, there were essentially no other solvent molecules remaining that could be considered as bulk solvent. Calculations also showed that the internuclear distance in these solutions supported the proposal that the ionic entity dominating in solution was the SShIP, and other evidence was adduced that confirmed the absence of Contact Ion Pairs at these concentrations. The parameters of the shape of the vibrational correlation functions of all three species are reported. The parameters of intramolecular anharmonic coupling between the potential surfaces in AN and the dynamics of the intermolecular environment fluctuations and intermolecular energy transfer are presented. These results will assist investigations made at higher and lower concentrations, when additional species and interactions with AN molecules will be present.

Non-Markov state model of peptide dynamics

A hidden Markov state model has been applied to classical molecular dynamics simulated small peptide in explicit water. The methodology allows increasing the time resolution of the model and describe the dynamics with the precision of 0.3 ps (comparing to 6 ps for the standard methodology). It also permits the investigation of the mechanisms of transitions between the conformational states of the peptide. The detailed description of one of such transitions for the studied molecule is presented. © 2012 Elsevier B.V. All rights reserved.

Polarization dynamics of bound state solitons in a carbon nanotubes mode locked erbium doped fiber laser

Optical solitons are important in the modern photonics. Passively mode locked erbium doped fiber lasers provide a neat platform to study soliton dynamics. Soliton interaction dynamics is important for various applications and has quite different manifestations, including e.g. such as bound state solitons [1], soliton rains [2]. Soliton interactions have been observed with different mode locking approaches such as figure-of-eight [3] and nonlinear polarization rotation [4]. Carbon nanotubes (CNT) have recently been widely applied as an efficient saturable absorber for passively mode locked fiber lasers. We have recently studied the polarization dynamics in a CNT mode locked vector soliton erbium doped fiber laser [5]. So far, the polarization dynamics of bound state solitons have yet to be investigated. In this report, we present a wide range of polarization dynamics of bound state solitons generated in a CNT mode locked erbium doped fiber laser. The fiber laser consists of ∼ 2 m highly doped erbium fiber (Liekki Er80-8/125) as the gain medium, an optical isolator to ensure unidirectional oscillation anda 980 nm laser diode is used to pump the gain through the 1550/980 nm wavelength division multiplexer. A fused 10:90 coupler is used to couple 10 % of the light out of the laser cavity and two in-line polarization controllers (NewPort) are used to control the birefringence of the cavity and polarization of the pump light respectively. The total cavity length is ∼ 7.8 m indicating a 25.7 MHz fundamental repetition rate. © 2013 IEEE.