ABSTRACT
Photonic heterostructures with codable properties have shown great values as versatile information carriers at the micro and nanoscale. These heterostructures are typically prepared by a step-by-step growth or post-functionalization method to achieve varied emission colors among different building blocks. In order to realize high-throughput and multivariate information loading, we report here a strategy to integrate polarization signals into photonic heterojunctions. A U-shaped di-Pt(II) complex is assembled into highly-polarized yellow-phosphorescent crystalline microrods (Y-rod) by strong intermolecular Pt···Pt interaction. Upon end-initiated desorption of the incorporated CH2Cl2 solvents, Y-rod is transformed in a domino fashion into tri-block polarized photonic heterojunctions (PPHs) with alternate red-yellow-red emissions or red-phosphorescent microrods (R-rod). The red emissions of these structures are also highly polarized; however, their polarization directions are just orthogonal to those of the yellow phosphorescence of Y-rod. With the aid of a patterned mask, R-rod is further programmed into multi-block PPHs with precisely-controlled block sizes by side-allowed adsorption of CH2Cl2 vapor. X-ray diffraction analysis and theoretical calculations suggest that the solvent-regulated modulation of intramolecular and intermolecular excited states is critical for the construction of these PPHs.
ABSTRACT
Circularly polarized luminescence (CPL)-active molecular materials have drawn increasing attention due to their promising applications for next-generation display and optoelectronic technologies. Currently, it is challenging to obtain CPL materials with both large luminescence dissymmetry factor (glum) and high quantum yield (Φ). A pair of enantiomeric N N C-type Pt(II) complexes (L/D)-1 modified with chiral Leucine methyl ester are presented herein. Though the solutions of these complexes are CPL-inactive, the spin-coated thin films of (L/D)-1 exhibit giantly-amplified circularly polarized phosphorescences with |glum| of 0.53 at 560â nm and Φair of ~50 %, as well as appealing circular dichroism (CD) signals with the maximum absorption dissymmetry factor |gabs| of 0.37-0.43 at 480â nm. This superior CPL performance benefits from the hierarchical formation of crystalline fibrillar networks upon spin coating. Comparative studies of another pair of chiral Pt(II) complexes (L/D)-2 with a symmetric N C N coordination mode suggest that the asymmetric N N C coordination of (L/D)-1 are favorable for the efficient exciton delocalization to amplify the CPL performance. Optical applications of the thin films of (L/D)-1 in CPL-contrast imaging and inducing CP light generation from achiral emitters and common light-emitting diode lamps have been successfully realized.
ABSTRACT
Room-temperature phosphorescence (RTP) two-dimensional (2D) organic-inorganic hybrid perovskites (OIHPs) that possess superior stability and efficient triplet energy transfer between inorganic parts and organic cations have been seen as promising materials in optoelectronic devices. However, the development of RTP 2D OIHP-based photomemory has not been explored yet. In this work, the spatially addressable RTP 2D OIHPs-based nonvolatile flash photomemory is first investigated to explore the function of triplet excitons in elevating the performance of photomemory. Thanks to the triplet excitons generated in RTP 2D OIHP, extremely low photo-programming time of 0.7 ms, multilevel behavior of minimum 7 bits (128 levels), remarkable photoresponsivity of 19.10 AW-1 and significantly low power consumption of 6.79 × 10-8 J per bit can be achieved. The current study provides a new prospective in understanding triplet excitons function in nonvolatile photomemory.
ABSTRACT
Efficient diode-pumped passively Q-switched Nd:YVO4 yellow and orange lasers are developed with the pulse pumping scheme and the intracavity stimulated Raman scattering (SRS) and second harmonic generation (SHG). A Np-cut KGW is exploited in the SRS process to generate the yellow 579 nm laser or the orange 589 nm laser in a selectable way. The high efficiency is achieved by designing a compact resonator to include a coupled cavity for intracavity SRS and SHG and to provide a focused beam waist on the saturable absorber for reaching an excellent passive Q-switching. The output pulse energy and peak power can reach 0.08 mJ and 50 kW for the orange laser at 589 nm. On the other hand, the output pulse energy and peak power can be up to 0.10 mJ and 80 kW for the yellow laser at 579 nm.
ABSTRACT
We have used ab initio molecular dynamics (AIMD) simulations to study the interaction of water with the NaCl surface. As expected, we find that water forms several ordered hydration layers, with the first hydration layer having water molecules aligned so that oxygen atoms are on average situated above Na sites. In an attempt to understand the dissolution of NaCl in water, we have then combined AIMD with constrained barrier searches, to calculate the dissolution energetics of Na(+) and Cl(-) ions from terraces, steps, corners and kinks of the (100) surface. We find that the barrier heights show a systematic reduction from the most stable flat terrace sites, through steps to the smallest barriers for corner and kink sites. Generally, the barriers for removal of Na(+) ions are slightly lower than for Cl(-) ions. Finally, we use our calculated barriers in a Kinetic Monte Carlo as a first order model of the dissolution process.
ABSTRACT
A 100-year history of human and natural disturbances in southwestern Taiwan was reconstructed using a suite of molecular markers in four dated sediment cores from the upper slope region off the Gaoping River mouth. Trends in polycyclic aromatic hydrocarbons (PAHs) tracked Taiwan's industrialization/urbanization starting in the 1970s, and the enactment of environmental regulatory policies thereafter. The predominant pyrogenic sources include vehicular, smelter, and coal combustion but spatial differences are observed among sub-regions of the shelf. Profiles of lignin oxidation products (LOPs) point to a significant increase in terrestrial organic matter inputs driven by land development after the 1970s. Low lignin diagenetic signature ratios [(Ad/Al)v] in all sediments suggest quick transport of fresh plant material from land to sea via mountainous rivers. Shifts in PAHs, LOPs, and radionuclides in recent sediments reveal the deposition of turbidites resulting from typhoon-induced floods. Multiproxy analysis illustrates the interplay between anthropogenic activities and natural processes.
Subject(s)
Environmental Monitoring/methods , Environmental Pollution/history , Geologic Sediments/chemistry , Polycyclic Aromatic Hydrocarbons/analysis , Water Pollutants, Chemical/analysis , Weather , Environmental Monitoring/statistics & numerical data , Environmental Pollution/statistics & numerical data , History, 20th Century , History, 21st Century , Humans , Rivers , TaiwanABSTRACT
The dissolution of NaCl has been systematically investigated by employing ab initio molecular dynamics (AIMD) on different NaCl nanocrystals as well as on a surface system immersed in water. We discovered a complex dissolution process simultaneously involving multiple ions initiated at the corner sites of the crystal. Our simulations indicated a difference in the dissolution rates of sodium and chlorine. While sodiums readily became partially solvated, chlorines more frequently transitioned into the fully solvated state leading to an overall greater dissolution rate for Cl. We determined that this difference arises due to faster water mediated elongations of individual ionic bonds to Na, but a significantly slower process for the last bond in comparison to Cl. In an attempt to investigate this phenomenon further, we performed metadynamics based free energy simulations on a surface slab presenting corner sites similar to those in cubic crystals, aiming to extract the dissolution free energy profile of corner ions. In qualitative agreement with the nanocrystal simulations, this revealed a shallower first free energy minimum for Na, but no statistically significant difference in the corresponding barriers and inconclusive results for the latter stage. Finally, simulations of smaller NaCl crystals illustrated how dissolution proceeds beyond the point of crystal lattice collapse, highlighting the strength of solvated ion interactions.
ABSTRACT
The dissociation of H(2) on Ti-covered Al surfaces is relevant to the rehydrogenation and dehydrogenation of the NaAlH(4) hydrogen storage material. The energetically most stable structure for a 1/2 monolayer of Ti deposited on the Al(100) surface has the Ti atoms in the second layer with a c(2 × 2) structure, as has been confirmed by both low-energy electron diffraction and low-energy ion scattering experiments and density functional theory studies. In this work, we investigate the dynamics of H(2) dissociation on a slab model of this Ti/Al(100) surface. Two six-dimensional potential energy surfaces (PESs) have been built for this H(2) + Ti/Al(100) system, based on the density functional theory PW91 and RPBE exchange-correlation functionals. In the PW91 (RPBE) PES, the lowest H(2) dissociation barrier is found to be 0.65 (0.84) eV, with the minimum energy path occurring for H(2) dissociating above the bridge to top sites. Using both PESs, H(2) dissociation probabilities are calculated using the classical trajectory (CT), the quasi-classical trajectory (QCT), and the time-dependent wave-packet methods. We find that the QCT H(2) dissociation probabilities are in good agreement with the quantum dynamics results in the collision energy range studied up to 1.0 eV. We have also performed molecular beam simulations and present predictions for molecular beam experiments. Our molecular beam simulations show that H(2) dissociation on the 1/2 ML Ti/Al(100) surface is an activated process, and the reaction probability is found to be 6.9% for the PW91 functional and 1.8% for the RPBE at a nozzle temperature of 1700 K. Finally, we have also calculated H(2) dissociation rate constants by applying transition state theory and the QCT method, which could be relevant to modeling Ti-catalyzed rehydrogenation and dehydrogenation of NaAlH(4).
ABSTRACT
The widespread adoption of hydrogen as an energy carrier could bring significant benefits, but only if a number of currently intractable problems can be overcome. Not the least of these is the problem of storage, particularly when aimed at use onboard light-vehicles. The aim of this overview is to look in depth at a number of areas linked by the recently concluded HYDROGEN research network, representing an intentionally multi-faceted selection with the goal of advancing the field on a number of fronts simultaneously. For the general reader we provide a concise outline of the main approaches to storing hydrogen before moving on to detailed reviews of recent research in the solid chemical storage of hydrogen, and so provide an entry point for the interested reader on these diverse topics. The subjects covered include: the mechanisms of Ti catalysis in alanates; the kinetics of the borohydrides and the resulting limitations; novel transition metal catalysts for use with complex hydrides; less common borohydrides; protic-hydridic stores; metal ammines and novel approaches to nano-confined metal hydrides.
ABSTRACT
Based on a slab model of H(2) dissociation on a c(2 × 2) structure with Ti atoms in the first and third layers of Al(100), a six-dimensional (6D) potential energy surface (PES) has been built. In this PES, a molecular adsorption well with a depth of 0.45 eV is present in front of a barrier of height 0.13 eV. Using this PES, H(2) dissociation probabilities are calculated by the classical trajectory (CT), the quasiclassical trajectory (QCT), and the time-dependent wave-packet (TDWP) method. The QCT study shows that trajectories can be trapped by the molecular adsorption well. Higher incident energy can lead to direct H(2) dissociation. Vibrational pre-excitation is the most efficient way to promote direct dissociation without trapping. We find that both rotational and vibrational excitation have efficacies close to 1.0 in the entire range of incident energies investigated, which supports the randomization in the initial conditions making the reaction rate solely dependent on the total (internal and translational) energy. The H(2) dissociation probabilities from quantum dynamics are in reasonable agreement with the QCT results in the energy range 50-200 meV, except for some fluctuations. However, the TDWP results considerably exceed the QCT results in the energy range 200-850 meV. The CT reaction probabilities are too low compared with the quantum dynamical results.
ABSTRACT
We report on the first fabrication of a Cr-doped fiber using a drawing-tower method with Cr:YAG as the core of the preform. Both Cr3+ and Cr4+ ions coexist in the Cr-doped fiber, and the amplified spontaneous emission (ASE) spectrum shows a broadband emission of 1.2 to 1.55 mum which can not be realized by using currently available fiber amplifiers. This indicates that the new Cr-doped fibers have the potential for being used as a broadband fiber amplifier to cover the bandwidth of the entire 1.3-1.6 mum range which exhibit 300 nm usable spectral bands.
ABSTRACT
Glass-clad Cr4+:YAG crystal fiber is demonstrated by a codrawing laser-heated pedestal growth method. As much as 2.45 mW of superwideband amplified spontaneous emission (ASE) is generated in the optical fiber communication band with a 3-dB width of 240 nm. The simulation indicates that the ASE power could be in excess of 20 dBm for a 5-microm-diameter core at a pump power of 2.5 W.