Molecular Geometry Optimization, Two-Photon Absorption and Electrochemistry of New Diphenylethylene Derivatives Linking with Benzophenone Moiety Through Ether Covalent Bond

This paper presents the molecular geometry optimization, two-photon absorption and electrochemistry of new dyes containing benzophenone part, including 4-(p-benzoyl-benzyloxy)yl-4'-nitro-diphenylethylene (C1), 4-[N-methyl-N-(2-(p-benzoyl-benzyloxy)yl-ethyl]-4'-nitro-diphenylethylene (C2), 4-[N-ethyl-N-(2-(p-benzoyl-benzyloxy)yl-ethyl]-4'-nitro-diphenylethylene (C3), and 4-N, N-bis[(2-(p-benzoyl-benzyloxy)yl-ethyl]-4'-nitro-diphenyl ethylene (C4). The molecular structural parameters show that the coplanarity of diphenylethylene moiety is diminished in the excited state for C1, while it is enhanced for C2, C3 and C4. The electron density distribution of frontier orbital suggests that the derivatives exhibit (π, π) transition with internal charge transfer character, and the extent of charge transfer of C2, C3 and C4 is larger than that of C1. The derivatives display remarkable two-photon absorption (TPA) induced up-converted emission under 800 nm Ti: Sapphire femtosecond laser excitation. The maximal TPA emission wavelength of C2, C3 and C4 is red-shifted with respect to that of C1. TPA cross sections of C2, C3 and C4 are larger than those of C1. The cyclic voltammograms and the fluorescence lifetimes of the derivatives were determined and discussed.     

A Comprehensive Investigation on the Cooperative Branch Effect on the Optical Properties of Novel Conjugated Compounds

This paper presents a variety of conjugated derivatives with different number of arms (4-styryl-triphenylamine: C1, 4, 4′-di-styryltriphenylamine: C2, 4, 4′, 4″-tri-styryltriphenylamine: C3). The linear absorption and fluorescence maxima and the molar extinction coefficients are in the order of C1<C2<C3 in various solvents. Two-photon absorption (TPA) up-converted emission of the derivatives were determined with Ti:sapphire femtosecond laser. The maximal TPA emission wavelength and the two-photon absorption cross section of the derivatives are also in the order of C1<C2<C3 in various solvents. The dipole moment changes of the derivatives between the excited state and the ground state were estimated from experiment, and they are in the order of C1<C2<C3, which is confirmed further by the molecular geometry optimization of the derivatives. The electron density distribution and the energy levels of the frontier orbital of the derivatives were analyzed. The cyclic voltammograms of the derivatives were performed and discussed.     

Synthesis and Spectroscopy of Novel Branched Fluorescent Dyes Containing Benzophenone Parts and the Possibility as Fluorescence Probes

This paper describes a new fluorescent family of branched dyes containing benzophenone unit including 4-N, N-diphenylamino-4??-phenacyl-stilbene (C1), 4,4??-di(4-benzoylphenylethylene)yl-triphenylamine (C2) and 4,4??,4??-tri(4-benzoylphenylethylene)yl-triphenylamine (C3). Benzophenone part is coupled with core through C?CC double bond. The chemical structures of the derivatives are characterized with ¹H and ¹³C nuclear magnetic resonance and elemental analysis. Strong ?ШC?? stacking interactions are discovered with the analysis of the X-ray crystallographic data of C1. The absorption maxima and emission maxima of the derivatives exhibit gradual bathochromic shift from C1 to C3. The optical density of C1, C2 and C3 are shown to be related to the number of branches. The changes of dipole moments between the excited and ground states for C1, C2 and C3 were estimated to be 4.356, 8.091 and 8.479 Derby, respectively by Lippert equation, confirming that the internal charge transfer (ICT) dominates the process of excited singlet state. The possibility as fluorescence probes of the derivatives on the estimation of what region of micelles interacting with samples was evaluated.     

Experimental and theoretical studies on the one‐photon and two‐photon properties of a series of carbazole derivatives containing styrene

Symmetric‐type carbazole derivatives show great potential for application in two‐photon absorption (TPA) materials and organic light‐emitting diodes. The absorption spectra and fluorescence emission spectra of three different N‐alkyl symmetric‐type carbazole derivatives were investigated. The density functional theory (DFT) time‐dependent‐DFT//Becke, three‐parameter, Lee–Yang–Parr/6‐31 G* method has been used to theoretically study one‐photon absorption properties. The computational results are in good agreement with the available experimental values. The two‐photon excited fluorescence of the compounds was surveyed by 120 fs pulse at 790 nm Ti: sapphire laser operating at 1 kHz repetition rate. Two‐photon excited fluorescence was obtained in the range of 380–600 nm, and TPA cross‐sections were calculated. The TPA properties of the series of compounds were investigated by the ZINDO/single and double electronic excitation configuration interaction method. The influence of the chemical structure of the compounds on two‐photon optical properties was discussed. The results show how the different changes in one‐photon absorption and TPA properties on the basis of lengthening the conjugated bridge and the different carbazole N‐alkyl substituents are attributed to the transition dipole moment in the excited process. Copyright © 2011 John Wiley & Sons, Ltd.     

Femtosecond pulsed laser deposition of Ge quantum dot growth on Si(1 0 0)-(2 × 1)

Ge quantum dots were grown on Si(1 0 0)-(2 × 1) by femtosecond pulsed laser deposition at various substrate temperatures using a femtosecond Ti:sapphire laser. In situ reflection high-energy electron diffraction and ex situ atomic force microscopy were used to analyze the film structure and morphology. The morphology of germanium islands on silicon was studied at different coverages. The results show that femtosecond pulsed laser deposition reduces the minimum temperature for epitaxial growth of Ge quantum dots to ∼280 °C, which is 120 °C lower than previously observed in nanosecond pulsed laser deposition and more than 200 °C lower than that reported for molecular beam epitaxy and chemical vapor deposition.     

6,7-Difluoro-1,4-dihydro-1-methyl-4-oxo-3-quinolinecarboxylic Acid, a Newly Designed Fluorescence Enhancement-Type Derivatizing Reagent for Amino Compounds

A novel fluorescence enhancement-type derivatizing reagent for amino compounds, 6,7-difluoro-1,4-dihydro-1-methyl-4-oxo-3-quinolinecarboxylic acid (FMQC), was developed. FMQC reacts with aliphatic primary amino compounds to afford strong fluorescent derivatives having high photo-and thermo-stabilities. The FMQC derivatives of amino compounds showed 12–159 times higher fluorescence quantum efficiencies than those of FMQC in aqueous and polar organic media. Additionally, the absorption and fluorescence emission wavelength of the derivatives are red-shifted from those of FMQC. These differences in the fluorescence properties between FMQC and the fluorescent derivative enabled the simple and highly sensitive determination of amino compounds without removing any excess unreacted FMQC by using a simple spectrofluorometer as well as HPLC.     

Simultaneous three-photon-excited violet upconversion luminescence of Ce3+:Lu2Si2O7 single crystals by femtosecond laser irradiation

We found that Ce3+:Lu2Si2O7 single crystals could be excited at 800 nm by using a femtosecond Ti:sapphire laser. The emission spectra of Ce3+:Lu2Si2O7 crystals were the same for one-photon excitation at 267 nm as for excitation at 800 nm. The emission intensity of Ce3+:Lu2Si2O7 crystals was found to depend on the cube of the laser power at 800 nm, consistent with simultaneous absorption of three 800 nm photons. The measured value of the three-photon absorption cross section is sigma'3=2.44x10(-77) cm6 s2.     

Application of a femtosecond self-sustaining mode-locked Ti:sapphire laser to the field of laser scanning confocal microscopy

Developments in ultrafast Ti:sapphire laser technology can be applied in the investigation of nonlinear optical processes. We describe the application of a self-sustaining femtosecond Ti:sapphire laser as an illumination source in the field of confocal laser scanning fluorescence microscopy (LSM). We present spectra for various fluorescent stains under two-photon excitation and present LSM images of stained samples under mode-locked illumination. The potential for such a system as a non-destructive technique for studying live cells in biomedical research is discussed.     

Conical four-wave mixing in sodium vapour excited by femtosecond laser pulses

Broadband (sometimes exceeding 1500 cm^-1) red-shifted (with respect to the sodium 3S–3P transition frequency) conical emission has been observed with the pump wavelength tuned in the range between 540 and 589 nm. Such broadband emission was attributed to the generation and amplification of light at the Rabi sideband frequencies in the field of intense femtosecond laser pulses. It has been shown that the cone angle of the emitted radiation is determined by the process of four-wave mixing under the conditions of longitudinal (Cherenkov-type) phase matching. PACS 42.65.Ky; 42.65.Re; 42.50.Hz     

Laser-induced damage threshold of sapphire in nanosecond, picosecond and femtosecond regimes

The surface laser-induced damage threshold fluence of sapphire is determined under various experimental conditions concerning the material irradiation (femtosecond, picosecond and nanosecond temporal regimes) and preparation (surface state). The results are of interest for optimising laser micromachining processes and for robust operation of high-peak power femtosecond Ti:sapphire laser chains.     

Efficient two-photon absorption of CdSe-CdS/ZnS core-multishell quantum dots under the excitation of near-infrared femtosecond pulsed laser

We report that two-photon absorption (TPA) properties of semiconductor CdSe-core CdS/ZnS-multishell quantum dots (QDs) in toluene under excitation of femtosecond laser at 800 nm. The results show efficient TPA process and large TPA cross section of three types of size QDs, which is 1900, 5710, and 16060 GM (1 GM = 10⁻⁵⁰ cm⁴ s photon⁻¹), respectively. TPA cross section dramatically increases with increased core size, showing a strong size-dependence effect. Furthermore, two-photon excitation (TPE) fluorescence intensity not only depends on TPA capacity, but also relies on improved quantum yield resulting from passivation of QD surface by different coated monolayers (MLs). These facts in combination with the narrow fluorescence bandwidth make these QDs as promising probes for multicolor two-photon microscopy.     

Two-color two-photon excitation of indole using a femtosecond laser regenerative amplifier

The fluorescence emission from indole resulting from two-color two-photon (2C2P) excitation with 400 and 800 nm wavelengths is observed, using the second harmonic and fundamental wavelength of a 800 nm 40 fs pulsed Ti:Sapphire femtosecond (fs) regenerative amplifier operating at a repetition rate of 1 kHz. By delaying one fs laser pulse relative to the other, the cross correlation of fluorescence is observed, which indicates the generation of 2C2P fluorescence signal in the experiment. The strongest 2C2P fluorescence emission characterized by the peak of cross correlation curve suggests optimal temporal overlap of the two fs laser pulses. The 2C2P fluorescence signal is linearly dependent on the total excitation intensity. The fluorescence signals with 400 nm and 800 nm irradiation alone are also demonstrated and discussed in this paper.     

Nonlinear two-photon absorption properties induced by femtosecond laser with the films of two novel anthracene derivatives

Two novel anthracene derivatives containing 4-vinylpyridine (FPEA) and 2-vinylpyridine (TPEA) poly(methyl methacrylate) films are prepared on quartz glass substrates. Their nonlinear absorption properties are investigated by using a 120-fs, 800-nm Ti:sapphire femtosecond pulsed laser operating at a 1-kHz repetition rate. The unique nonlinear absorption properties of these new compounds are observed by utilizing a Z-scan system. These two-photon absorption (TPA) properties are proven by the two-photon fluorescence excited at 800 nm. The FPEA and TPEA films have nonlinear TPA coefficients of 0.164 and 0.148 cm/GW and the TPA cross sections of 3.345 × 10-48 and 3.081 × 10-48 cm4 ·s/photon, respectively. The influence of the chemical structures on the nonlinear TPA properties of the compounds is also discussed. The highly nonlinear TPA activities of the films implied that the new anthracene derivatives are suitable materials with promising applications in super-high-density three-dimensional data storage and nano- or microstructure fabrication.     

Efficient generation of vibrational stimulated Raman emission in the ultraviolet region using a femtosecond pump beam

The third harmonic emission (261 nm, 30 μJ) of a femtosecond Ti:sapphire laser is focused into molecular hydrogen to generate vibrational stimulated Raman emission. High-order emission lines are efficiently generated by using a high-beam-quality nearly-transform-limited laser and high-pressure hydrogen (40 atm) as a Raman medium.     

High resolution spectra of the red fluorescence in chemical oxygen-iodine laser

In our chemical oxygen-iodine laser(COIL)experiments we accidentally ob-served relatively strong red fluorescence while setting a hot metal wire in the cavity.The in-tensity of such emission is 2～3 orders of magnitude stronger than the initial O_2(~1A)dimerfluorescence.The fluorescence spectrum was measured with OMA and Bomem FT spectrome-ter respectively and the highest resolution of the measurement is 0.1cm~(-1).The emission maycome from O_4 molecules or an isomer of Cl_2O_2.     

Two-photon absorption and nonlinear optical properties of a new organic dye PSPI

Trans-4-[p-(pyrrolidinyl)styryl]-N-methylpyridinium iodide (abbreviated as PSPI thereafter) is a two-photon absorption (TPA) dye newly synthesized by our research group. It possesses much larger TPA cross-section and much stronger upconversion fluorescence emission than those of common organic dye (such as rhodamine) when excited with near infrared (IR) radiation. TPA spectrum and upconversion efficiency spectrum of HEASPI solution at various wavelengths were measured. There is 34 nm blue shift for the central wavelength of the TPA induced absorption peak compared with two times of the linear absorption peak. The biggest molecular TPA cross-section σ₂^′ is 2.85×10⁻⁴⁷ cm⁴ s/photon at 930 nm. At 1064 nm, σ₂^′ is 3.12×10⁻⁴⁸ cm⁴ s/photon. The highest efficiency is 3.9% at 1010 nm, whereas 2.9% at 1064 nm. Its optical power limiting properties at 930 nm have also been illustrated.     

飞秒激光在双折射微结构光纤中模式控制的四波混频效应的实验研究

利用飞秒激光脉冲在长度为10cm，包层具有大空气比的双折射微结构光纤中通过高阶模相位 匹配的四波混频获得了波长可调谐的反斯托克斯波.实验中脉冲宽度为35fs，中心波长820nm ，单脉冲能量4nJ的飞秒激光脉冲耦合到长轴直径为5μm，短轴为46μm的双折射微结构光 纤中.在高阶模传输情况下，通过调制耦合光的偏振方向，获得了具有不同中心波长的反斯 托克斯波.通过对比分析，讨论了输入光的偏振态对双折射微结构光纤中高阶模式下四波混 频效应的影响情况.理论计算分析很好的解释了实验结果. 关键词： 微结构光纤 飞秒脉冲激光 四波混频     

高峰值功率固体飞秒激光振荡器技术的进展

总结了目前几种可产生兆瓦级（10^6W)峰值功率的飞秒（10^-15s)掺钛蓝宝石激光器的发展状况，分析了这类激光器相应的腔结构，讨论了相关的特点以及在实验上的应用前景。     

Studies on Absorption and Emission Characteristics of Inclusion Complexes of Some 4-Arylidenamino-5-phenyl-4H-1, 2, 4-triazole-3-thiols

The inclusion complexes of a series of 4-arylidenamino-5-phenyl-4H-1, 2, 4-triazole-3-thiols have been prepared with β-cyclodextrin. The compounds and their inclusion complexes have been characterized by studying their physical and spectral properties. The thermodynamic stability constant and free energy of activation have been determined to know the stability of inclusion complexes and type of host-guest relation. Finally, absorption, excitation and emission spectra of the compounds (4-arylidenamino-5-phenyl-4H-1, 2, 4-triazole-3-thiols) and their inclusion complexes have been taken. It is found that inclusion complex formation brings about a drastic change in absorption and fluorescence characteristic (both excitation and emission spectra) of newly synthesized compounds.     

Absolute frequency measurement of an acetylene-stabilized laser at 1542 nm

The absolute frequency of an acetylene-stabilized laser at 1542 nm is measured at its second harmonic (771 nm) by use of a femtosecond optical comb based on a mode-locked Ti:sapphire laser. Frequency stability and reproducibility of the acetylene-stabilized laser are evaluated by the femtosecond comb with a H maser as a frequency reference. The absolute frequency of a laser diode stabilized on the P(16) transition of 13C2H2 is determined to be 194 369 569 383.6(1.3) kHz. The acetylene-stabilized laser serves as an important optical frequency standard for telecommunication applications.