CdSe/ZnS核-壳结构量子点的非线性光学吸收

利用开孔Z扫描技术研究了吸收峰分别为553 nm和503 nm的两种尺寸CdSe/ZnS核-壳结构量子点溶液的非线性吸收性质.对于532 nm,6 ns激光脉冲,两种材料均表现出饱和吸收向反饱和吸收转化的现象.数值模拟结果表明：当吸收峰波长大于激光波长时,饱和吸收过程由快、慢两种机制组成,分别对应基态载流子被激发至不同的激发态,而强光下的反饱和吸收与快过程相关;当吸收峰波长小于激光波长时,饱和吸收主要由快过程机制引起,强光下的反饱和吸收源自激发态吸收和双光子吸收.我们的研究结果表明半导体量子点是研制光开关和光限制器件的理想候选材料.     

Study of absorption spectrum and dynamics evaluation of the indocyanine‐green first singlet excited state

Excited state absorption and excited state dynamics of indocyanine‐green (ICG) dissolved in dymethyl sulfoxide were measured using white‐light continuum Z‐scan (WLCZScan) and white‐light continuum pump–probe (WLCPP) techniques. The excited state absorption spectrum, obtained through Z‐scan measurements, revealed saturable absorption (SA) for wavelengths longer than 630 nm, while reverse saturable absorption (RSA) appeared, as indicated by a band at approximately 570 nm. Both processes were modeled by a three‐energy‐level diagram, from which the excited state cross‐section values were determined. SA and RSA were also observed in pump–probe experiments, with a recovery time in the hundreds of picoseconds time scale due to the long lifetime of the first excited state of ICG. Such results contribute to the understanding of ICG optical properties, allowing application in photonics and medicine. Copyright © 2010 John Wiley & Sons, Ltd.     

Theoretical investigation on nonlinear absorption of multilevel organic molecular system in ns, ps and fs regime

The nonlinear absorption properties of organic materials in nanosecond (ns), picoseond (ps) and femtosecond (fs) regime were theoretically investigated by rate equations based on multilevel organic molecular system, respectively. The simulation results show that the RSA is mainly due to the absorption contribution of the triplet first excited state in the ns regime and that of the singlet first excited state in the ps regime, both of which are a third-order nonlinear phenomena. The RSA in fs regime is mainly due to the excited state absorption (ESA) induced by two-photon absorption (TPA), which is a fifth-order nonlinear phenomenon.     

掺Er3+玻璃的光限幅特性研究

利用波长为532 nm的皮秒脉冲激光,研究了掺Er3 玻璃的光限幅特性和反饱和吸收.当入射功率不断增加且超过一定阈值时,透射功率不再随着入射功率快速增大,而是逐渐趋向于较稳定状态,从而实现了对强激光的光限幅效应.进一步利用布居速率方程讨论了其机制并给出了激发态的吸收截面,结果表明激发态吸收是其主要的光限幅机理.     

Effects of solvent on nonlinear absorption properties of tetraphenylporphyrin compounds in the nanosecond regime

The nonlinear absorption properties of tetraphenylporphyrins (TPP) in different solvents and excitation intensities are investigated with nanosecond pulses by the Z-scan technique. The nonlinear absorption behaviour observed presents a distinct difference between in solvent mixtures and in pure solvents. A crossover from reverse saturable absorption (RSA) to saturable absorption (SA) and then again to RSA is observed with the increases of excitation intensity in chloroform and pyridine mixed solvents. However, porphyrin molecules in pure solvents show good RSA behaviour under the studied intensity range, no saturation absorption is observed with nanosecond excitation. Excited state absorption parameters and two-photon absorption coefficients are obtained by theoretical fit using rate equations for population densities in a seven-level energy scheme.     

罗丹明染料激发态吸收及非线性荧光效应研究

系统研究了罗丹明6G和罗丹明B的非线性吸收特性和荧光猝灭特性,结果表明它们在532nm的激光波长作用下,呈饱和吸收特性,在355nm的激光波长作用下呈现反饱和吸收特性,通过理论拟合得到了激发态吸收截面和能级寿命;并对荧光猝灭现象进行了解释,首次提出激发态吸收诱导荧光猝灭的理论.     

All-optical ultrafast logic gates based on saturable to reverse saturable absorption transition in CuPc-doped PMMA thin films

A detailed theoretical analysis of femtosecond transition from saturable (SA) to reverse saturable absorption (RSA) has been carried out in Copper-Phthalocyanine (CuPc)-doped polymethylmethacrylate (PMMA) thin films. The transition due to fifth-order effect of excited-state absorption induced two-photon process has been optimized with respect to intensity, concentration and nonlinear coefficients to design various all-optical logic gates, namely, OR and AND at lower intensities (SA region), XOR at the transition intensity, and the universal NAND and NOR at higher intensities (RSA region). The advantages of ultrafast operation, simplicity, tunability, high contrast, stability of CuPc-doped PMMA thin film, and the possibility to control and realize various logic operations in the same film at the same wavelength by only controlling the pulse intensity, instead of a pump-probe configuration, make them attractive for practical implementation.     

Nonresonant and Resonant Nonlinear Absorption of CdSe-Based Nanoplatelets

We present a comprehensive understanding of the nonlinear absorption characteristics of CdSe-based nanoplatelets(NPLs) synthesized by the solution-phase method and the colloidal atomic layer deposition approach through Z-scan techniques at 532 nm with picosecond pulses. The CdSe NPLs exhibit strong two-photon induced free carrier absorption(effective three-photon absorption) upon the nonresonant excitation, resulting in a remarkable optical limiting behavior with the limiting threshold of approximately 75 GW/cm~2. A nonlinear optical switching from saturable absorption(SA) to reverse saturable absorption(RSA) with increasing the laser intensity is observed when coating CdSe NPLs with a monolayer of CdS shell to realize the resonant absorption. The SA behavior originates from the ground state bleaching and the RSA behavior is attributed to the free carrier absorption.These findings explicitly demonstrate the potential applications of CdSe-based NPLs in nonlinear optoelectronics such as optical limiting devices, optical pulse compressors and optical switching devices.     

Picosecond nonlinear optical properties of cuprous oxide with different nano-morphologies

Cuprous oxide nanoclusters, microcubes and microparticles were successfully synthesized by a simple co-precipitation method. Phase purity and crystallinity of the samples were studied by using X-ray powder diffraction. Transmission electron microscopy (TEM) images show different morphologies like nanoclusters, microcubes and microparticles. For linear and nonlinear optical measurements, the as-synthesized Cu₂O with different morphologies were dispersed in isopropanol solution. The absorption spectrum recorded in the visible regions shows peaks that depend on the morphology of the particles and the peak shifts towards red region as one goes from nanoclusters to microparticles. Simple open-aperture Z-scan technique is used to measure nonlinear optical properties of cuprous oxide at 532 nm, 30 ps excitation at 10 Hz repetition rate. Cuprous oxide nanoclusters show reverse saturable absorption (RSA) behaviour, the microcubes and microparticles at a similar concentration exhibit saturable absorption (SA) type of behaviour at lower peak intensities and exhibit RSA within SA at higher peak intensities. The results show that the transition from SA to RSA can be ascribed to the two-photon absorption (TPA) process.     

基于密度泛函理论的肾上腺素分子的光谱分析

肾上腺素是一种神经和激素的传送体,研究肾上腺素分子的光谱和能级有助于了解其化学稳定性和药理作用。基于密度泛函理论（DFT）,利用Gaussian 09软件在B3LYP/6-311G（d,p）基组水平上对肾上腺素分子进行结构优化,采用含时密度泛函理论（TD-DFT）的PBE方法在def2tzvp基组水平上计算肾上腺素分子在气相中的前20个激发态,利用Multiwfn3.7（dev）软件绘制出其紫外光谱图并对激发性质进行分析。肾上腺素分子紫外光谱对应的主要跃迁是从基态分别到第1,2,4,8,15和16激发态的跃迁,其他的激发态的振子强度低于阈值0.03。理论计算得出肾上腺素的紫外光谱有两个吸收峰,分别位于206.23和273.92 nm,206.23 nm峰主要由基态跃迁到第16激发态形成,273.92 nm峰主要是基态跃迁到第2、4激发态形成,主要是由苯环上π→π*跃迁所产生,并与实验光谱吻合较好。对肾上腺素分子的激发态性质分析可知,上述吸收峰都是在最高占据轨道和最低空轨道的临近轨道跃迁产生的。利用密度泛函的PBE方法在6-311G（d, p）的基组水平上计算肾上腺素分子频率并绘制红外光谱,由振动分析可知,3 738和3 662 cm-1峰是由酚羟基O-H伸缩振动产生的特征吸收峰,3 715 cm-1峰是由醇羟基O-H伸缩振动产生的特征吸收峰,2 854 cm-1峰是由甲基的C18-H20键的伸缩振动产生的特征吸收峰,1 516和1 439 cm-1峰是苯环骨架的伸缩振动的特征吸收峰,1 279与1 057 cm-1峰分别是由C6-O10和C12-O23键伸缩振动产生的特征吸收峰,620 cm-1峰是N22-H17键摇摆振动的特征吸收峰。对比肾上腺素的实验红外光谱,发现理论光谱与实验光谱中各基团的特征吸收峰都较为明显且总体吻合较好。由于肾上腺素分子二聚体和多聚体之间形成氢键,分子间氢键的形成削弱了O-H键的强度,降低了能形成分子间氢键的羟基O-H的伸缩振动频率,从而导致实验光谱在3 500～2 500 cm-1之间呈现出一个宽峰。     

Analysis of the production and clusterization of iron atoms under pulsed laser photolysis of Fe(CO)5

Atomic-resonance absorption spectroscopy is used to study the production and loss of iron atoms under dissociation of the Fe(CO)₅ vapor in a quartz reactor that is induced by the pulses of the KrF excimer laser. Iron atoms populate the ground state owing to the quenching of the excited states generated in the course of the laser photolysis and are detected using the resonance absorption at a wavelength of 385.99 nm. The effective quenching rates are in good agreement with the known rates of the quenching of metastable iron atoms by the Fe(CO)₅ molecules. It is demonstrated that a loss of iron atoms is related to the recombination with dimer and trimer formation and the secondary atomic reactions with the Fe(CO)₅, CO, and FeCO molecules. The rates of the main elementary reactions responsible for the loss of iron atoms are determined using the comparison of the experimental results and kinetic simulation data.     

Reaction pathway and H/D kinetic isotope effects of the triple proton transfer in a 7‐hydroxyquinoline‐methanol complex in the ground state: A computational approach

Multiple proton transfer (PT) is an essential process in long‐range proton transport such as proton relay in enzymes. 7‐Hydroxyquinoline (7HQ) undergoes alcohol‐mediated PT in both the excited and ground states, and this system has been investigated as a biomimetic model. In the present study, the reaction pathway of triple PT in a 7HQ‐methanol cluster, 7HQ·(MeOH)₂, in the ground state has been investigated using density functional theory calculations to clarify the reaction mechanism and the origin of the experimentally observed kinetic isotope effect (KIE). The PT takes place in an asynchronous concerted fashion, in which the oxygen atom in 7HQ first accepts a proton from the directly hydrogen‐bonded MeOH. The rate constants and primary H/D KIEs have been estimated with canonical variational transition state theory in combination with the small curvature tunneling approximation. The tunneling effect on the PT rate is significant, and the KIE is much greater than 1 at room temperature. The rule of the geometric mean for the KIEs breaks down because of the asynchronicity in the motions of 3 protons and tunneling effect. In addition, the rate constant is smaller, the KIE is larger, and the activation energy is higher compared with the experimental values in heptane solution, suggesting that the PT dynamics in solution is governed by not only the intrinsic PT process but also thermal fluctuation of the solute and solvent molecules, which plays an important role in the configurational change of the 7HQ·(MeOH)₂ complex.     

Observation of simultaneous reverse saturation absorption and saturation absorption in silver nanoparticles incorporated into europium oxide thin film

In this work, nano silver clusters incorporated into europium oxide thin films at a level of 3.8% and 12.5% have been prepared by a vacuum evaporation method on glass and silicon substrates. Samples were investigated by X-ray fluorescence, X-ray diffraction, and linear and nonlinear optical absorption methods. The X-ray diffraction reveals that the Eu oxide of these samples remains amorphous after pre-annealing at 400 °C. The linear optical absorption of the samples shows surface plasmon resonance (SPR) phenomena, which varies with the Ag content of the samples. The optical nonlinear absorption properties of the prepared films were investigated using an open Z-scan technique with cw laser at wavelengths 476 nm and 514 nm. A changeover from reverse saturation absorption (RSA) to saturation absorption (SA) was observed. RSA is attributed to interband transition via two photon absorption. SA is attributed to plasmon bleach.     

Review of new experimental techniques for investigating random sequential adsorption

Burgeoning interest in random sequential adsorption (RSA) processes has led to a surge of theoretical results, but experimental work is lagging behind, due to a dearth of suitable techniques. This article reviews integrated-optical techniques for investigating the kinetics of RSA and related processes. The basic idea is to measure the phase shifts of guided waves, due to the adsorption of particles at the surface of a planar waveguide. The technique is very well suited to investigating 2-dimensional RSA, and can yield high-quality kinetic adsorption data, precise enough for rigorously testing theoretical predictions. The current state of the art allow adsorbed mass to be measured quasicontinuously with a precision of at least 1 ng/cm².     

TDDFT Investigation of the Electronic Structures and Photophysical Properties of Fluorescent Extended Styryl Push-Pull Chromophores Containing Carbazole Unit

Push-pull chromophores attached to carbazole based π-conjugating spacers bearing N-alkylamino donors, cyanovinyl and carbethoxy acceptors have been studied by the means of UV-Visible measurements. The intramolecular charge transfer (ICT) of these π-conjugated systems has also been tested by investigating the ability of the solute molecules to undergo shifts in their fluorescence emission maxima with increasing solvent polarity. Density Functional Theory [B3LYP/6-31G(d)] and Time Dependent Density Functional Theory [TD-B3LYP/6-31G(d)] computations have been used to have more understanding of the structural, molecular, electronic and photophysical parameters of push-pull dyes. The largest wavelength difference between the experimental and computed electronic absorption maxima was 45 nm. For emission, a largest difference of 61 nm was observed. The ground state and excited state dipole moments in different solvents were determined using experimental solvatochromic data and computed Onsager radii. The dipole moments of the molecules in the excited state were observed to be higher than in the ground state.     

Polarization phenomena in the transparency and adsorption effects induced by the field of counterpropagating waves

The physical processes that form the resonances of saturated absorption and magnetic scanning in the field of counterpropagating waves of an arbitrary intensity when their polarizations change are numerically simulated. The atomic transition with level moment J = 1 is used as an example to show that the anomalies in the experimental saturated absorption spectra are determined by the degree of opening of the atomic transition. In the case of magnetic scanning, the anomalies are caused by the magnetic coherence induced by the wave fields at the levels of the lower state rather than by its transfer from the excited states, as was proposed earlier.     

A theoretical study of the solvent shift to the transition in formaldehyde with an effective discrete quantum chemical solvent model including non-electrostatic perturbation

An effective solvent model with an explicit solvent representation is described. The modelled perturbation of the solute due to the discrete solvent molecules includes polarization and a non-electrostatic interaction. The latter depends on the overlap between the solute wave function and the solvent orbitals and approximately accounts for the restraint the Pauli principle puts on the space which the solute wave function is allowed to occupy, and consequently also models the exchange repulsion between solute and solvent. The wave function of the solute is a linear combination with variational coefficients of orthogonal states obtained with the complete active space state interaction (CASSI) method. With this model, the solvent shift to the n→ π* transition in hydrated formaldehyde is studied and the analysis of the results investigates the different contributions to the total shift; the non-electrostatic interaction is found to be of significance and capable of coupling with the electrostatic interaction in qualitatively different ways for the ground and first excited state. Solvent density distributions for hydrated formaldehyde are also reported.     

Solid-Surface Room Temperature Phosphorescence

Abstract

Luminescence can be defined as radiation emitted from atoms or molecules as they undergo a radiative transition from an excited state to a lower energy state. After the absorption of incident radiation, the emission of a photon during the radiative transition is called photoluminescence. The process of photoluminescence encompasses both fluorescence and phosphorescence.     

Steady and transient behavior of perylene under high pressure

Pressure can reduce the distances among atoms, thereby modifying the overall optical characteristics of molecules. In this article, the excited state behavior of perylene is carefully observed under isotropic pressure and non-complexing condition. In a steady state, absorption peak shows red shift and spectral width are broadened with pressure increasing, which is ascribed to the π-electron delocalization between molecules. In a transient state, the transition dynamics presents a wavelike tendency with pressure increasing because the shift of self-tapping exciton state is contrary to that of Y-state with pressure increasing. The results conduce to understanding the influence of inter-molecule interaction on excited state behavior with inter-molecule distance decreasing, which contributes to studying the materials under extreme condition.     

基于电子顺磁共振的ZnTPP激发态及其TEMPO各向异性的研究

为了研究卟啉类敏化剂的光致激发态能量转移和电子转移问题,本文基于紫外可见光谱仪和电子顺磁共振波谱仪,构建了以锌卟啉为研究对象的"锌卟啉-稳态自由基-二甲苯"实验体系.锌卟啉的紫外可见光谱显示,在可见光谱的B带和Q带出现明显的特征峰,是锌卟啉分子中电子由基态能级跃迁至激发态能级产生的.低温条件下受紫外可见光辐照的实验体系的电子顺磁共振波谱,检测到了稳态自由基四甲基哌啶氧化物的增强吸收电子顺磁共振波谱.根据分子激发态相关理论、光化学物理反应理论和化学诱导电子自旋极化理论对实验结果进行了分析,结果表明,四甲基哌啶氧化物稳态自由基电子顺磁共振波谱的增强吸收对应于锌卟啉光致激发态的能量转移和电子转移;四甲基哌啶氧化物在低温(143 K)下的电子顺磁共振波谱表现出的各向异性特征现象来源于氮氧自由基电子与氮核的各向异性超精细相互作用.