Mid-infrared laser-induced grating experiments of C2H4 and NH3 from 0.1–2 MPa and 300–800 K

Laser-induced thermal gratings (LITG) were generated in mixtures of ethylene and ammonia in nitrogen using mid-infrared laser radiation from a grating-tuned, low-pressure, pulsed (5 ms pulse width) CO₂ laser, and read out with a continuous wave Nd:YLF laser. The LITG signal intensity was measured as a function of pressure (0.1–2 MPa) and temperature (300–800 K, at 0.1 and 1 MPa) by tuning the laser to the accidental coincidences of the 10P(14) and 10R(6) emission lines with molecular absorption transitions of C₂H₄ and NH₃, respectively. Comparisons are made with theoretical predictions for the grating efficiency from a simple thermalization model. A theoretical comparison of the temporal LITG signal response for three excitation pulse shapes – a delta function, a realistic pulse, and a square wave is presented. Furthermore, it is shown that for NH₃, most of the decrease of the LITG signal intensity with increasing temperature is due to the corresponding decrease in fractional molecular absorption of the pump beam radiation. The diagnostic capabilities of the mid-infrared LITG experiment is demonstrated for spatially resolved ethylene measurements with long laser pulses in a premixed stoichiometric CH₄–air flame at atmospheric pressure. Received: 17 March 2000 / Revised version: 23 March 2000 / Published online: 13 September 2000     

Nonlinear optical characteristics of carbon disulfide

The nonlinear refractive index γ of CS₂ is studied using laser pulses of various durations (from 110 fs to 75 ns). It is found that γ increases with increasing pulse duration within the picosecond region (from (3 ± 0.6) × 10^?15 cm² W^?1 at 110 fs to (3.5 ± 0.7) × 10^?14 cm² W^?1 at 75 ns) due to orientational nonlinearities. Variations in the sign of γ caused by the thermal effect at different pulse durations and repetition rates are analyzed. It is demonstrated that the fast electronic component, the component associated with molecular processes, causing positive nonlinear refraction, and the acoustic component, responsible for negative nonlinear refraction, manifest themselves simultaneously. The results of a study of the nonlinear absorption of carbon disulfide are presented. The two-and three-photon absorption coefficients of CS₂ are determined to be (5 ± 1.5) × 10^?11 cm W^?1 and (2.8 ± 0.8) × 10^?23 cm³ W^?2, respectively.     

Fabrication of surface relief gratings on transparent dielectric materials by two-beam holographic method using infrared femtosecond laser pulses

Fabrication of surface relief-type gratings in transparent dielectrics, which are hard to machine, has been achieved by a holographic technique using two infrared femtosecond (fs) pulses from a mode-locked Ti:sapphire laser. The present method can be applied for a variety of transparent dielectrics, Al₂O₃ (sapphire), TiO₂, ZrO₂, LiNbO₃, SiC, ZnO, CdF₂, MgO, CaF₂ crystals, and SiO₂ glass. It is found that the grating formation is due primarily to laser ablation processes. Planar surface relief gratings can be fabricated by colliding two fs laser pulses on the surface of substrates which move at a constant speed, synchronized with the laser repetition rate. Received: 1 March 2000 / Published online: 7 June 2000     

Third-order nonlinear optical response in transparent solids using ultrashort laser pulses

The third-order optical nonlinearity, χ ⁽³⁾, is measured in transparent glasses (BK7 and fused silica) and crystals (BaF₂ and quartz) using 36-fs, 800-nm laser pulses and the optical Kerr gate (OKE) technique; values are found to lie in the range 1.3–1.7×10^-14 esu, in accordance with theoretical estimates. We probe the purely electronic response to the incident ultrashort laser pulse in fused silica and BK7 glass. In BaF₂ and quartz, apart from the electronic response we also observe contribution from the nuclear response to the incident ultrashort pulses. We observe oscillatory modulations that persist for ～400 fs. The response of the media (glasses and crystals) to ultrashort pulses is also measured using two-beam self-diffraction; the diffraction efficiency in the first-order grating is measured to be in the range of 0.06–0.13 %. Third harmonic generation due to self-phase matching in the transient grating geometry is measured as a function of temporal delay between the two incident ultrashort pulses, yielding the autocorrelation signal.     

布里渊增强非简并四波混频

在CS₂介质中观测到由声波引起的布里渊增强非简并四波混频(NFWM)和由分子取向栅产生的瑞利型NFWM.研究发现,分子取向栅与声波之间并不是相互独立的,声波的存在会破坏瑞利型NFWM和布里渊增强NFWM极化之间的相位关系. 关键词： 四波混频 布里渊散射 瑞利散射     

Polarization dependence of optical Kerr effect in metallophthalocyanine-doped inorganic-organic hybrid materials

Ultrafast optical Kerr effect of metallophthalocyanine-doped inorganic-organic materials was investigated using a femtosecond optical Kerr shutter at wavelength of 800 nm. Experimental results showed that the dependence of the Kerr signals on the polarization angle between the pump beam and the probe beam could be controlled by changing the pump-probe intensity ratio. The pump-intensity dependence of the polarization characters of the Kerr signals probably arose from the contribution of light induced transient grating (LITG) to the Kerr signals.     

Excitation wavelength dependence and magnetic field effect on aerosol particle formation from a gaseous mixture of carbon disulphide and glyoxal

Upon excitation of carbon disulphide (CS₂) molecules under UV light irradiation at 313?nm a gaseous mixture of CS₂ and glyoxal deposited sedimentary aerosol particles only. The nucleation process of the aerosol particles was investigated by measuring the He–Ne laser light intensity scattered by the aerosol particles formed under light irradiation at 313?nm, and the chemical structure of the sedimentary particles was analysed by measuring the FT-IR and X-ray photoelectron spectra. On application of a magnetic field of up to 5?T, the nucleation process was decelerated and the chemical species originating from CS₂ were less abundant. The results were compared with those obtained under visible light irradiation at 435.8?nm reported previously. Chemical reactions between CS₂ and glyoxal molecules, which were responsive to the magnetic field, are discussed briefly.     

A new distyrylbenzene derivative with Weinreb amide functionality: An efficient laser dye and nonlinear optical material

We report here the synthesis of a distyrylbenzene derivative with end substituent as Weinreb amide. This Weinreb amide-based distyrylbenzene (WADSB) gives indications of highly efficient laser dye as well as a nonlinear optical medium. The photophysical parameters of the dye are given here. The lasing spectra of the dye have been measured in a cuvette configuration. The third-order nonlinear susceptibility has been measured by laser-induced transient grating technique (LITG). A comparison with the existing standard molecules shows that it is a comparably an efficient lasing material as well as an efficient nonlinear optical material at the pump wavelength of 355 nm.     

水溶性CdTe量子点的三阶光学非线性极化特性

利用超短脉冲Z扫描技术和光学Kerr效应研究了以巯基丙酸为稳定剂的CdTe量子点水溶液的三阶光学非线性极化特性. 在532nm,30ps和800nm,130fs脉冲激光激发下, 发现分别具有正负相反取值的三阶光学非线性折射率,自由载流子吸收和双光子吸收分别是这两种脉冲激光激发下三阶光学非线性吸收的起因. 测量得到CdTe量子点的三阶光学非线性极化率约为CS₂的32倍, 在520—700nm光谱区的CdTe量子点的光学响应时间小于400fs. 关键词： CdTe量子点(QDs) Z扫描 三阶光学非线性极化特性 双光子吸收     

Photon echo peak shift experiments in the UV: p-terphenyl in different solvents

In this article we present a new photon echo set-up operating in the UV range and our first results of photon echo peak shift (PEPS) experiments of a small non-polar dye molecule, p-terphenyl (pTP), in three different solvents: ethanol, methanol and 2-propanol. The experiments show the feasibility of UV transient grating and photon echo measurements and highlight the sensitivity of this technique for the study of non-polar solvation dynamics. The transient grating experiments indicate a relaxation of the ground state hole of about 6 ps. The photon echo experiments show that while electronic dephasing occurs on timescales shorter than 100 fs, solvation dynamics timescales are in the picosecond regime, in agreement with the literature.     

Time‐resolved spectroscopic and density functional theory investigation of the photochemistry of suprofen

The photochemistry of suprofen (SPF) was investigated by femtosecond transient absorption (fs‐TA), resonance Raman (RR) and nanosecond time‐resolved resonance Raman (ns‐TR³) spectroscopic methods to gain additional information so as to better elucidate the possible photochemical reaction mechanism of suprofen in several different solvents. In neat acetonitrile (MeCN), the fs‐TA and ns‐TR³ experimental data indicated that the lowest lying excited singlet state S₁ (nπ*) underwent an efficient intersystem crossing process (ISC) to the excited triplet state T₃ (ππ*), followed by an internal conversion (IC) process to T₁ (ππ*). In the aqueous solution, a triplet biradical species (³ETK‐1) was obtained as the product of a decarboxylation process from triplet suprofen anion (³SPF⁻) and the reaction rate of the decarboxylation process was determined by the concentration of H₂O. A protonation process for ³ETK‐1 leads to formation of a neutral species (³ETK‐3) that was directly observed by ns‐TR³ spectra, then this ³ETK‐3 species decayed via ISC process to generate final product. Copyright © 2014 John Wiley & Sons, Ltd.     

液芯光纤中溶液吸收和荧光的性质对CS2受激拉曼散射阈值的影响

利用液芯光纤技术研究了不同浓度的β-Carotene的CS₂溶液的吸收与荧光的特性对CS₂的一、二阶Stokes谱线阈值的影响.实验发现随溶液浓度(10^-8—10^-6 mol/L)增加，CS₂的一阶Stokes谱线的激发阈值相对变高；并且与纯CS₂芯液的受激拉曼散射相比较，在低抽运能量激发下，就观察到CS₂的二阶Stokes谱线.这主要是由于在CS₂的受激拉曼谱线产生的过程中，β-Carotene的CS₂溶液的吸收和荧光共同影响了CS₂的一、二阶Stokes谱线的阈值.我们进行了理论上的拟合与分析，其结果与实验符合很好. 关键词： 2受激拉曼散射阈值')" href="#">CS₂受激拉曼散射阈值 液芯光纤 吸收与荧光     

掺杂CeO2的75TeO2-25Nb2O5-5ZnO飞秒激光诱导瞬态光栅的研究

用泵浦探测技术研究了掺杂CeO₂的75TeO₂-25Nb₂O₅-5ZnO玻璃在飞秒激光诱导的瞬态光栅多级自衍射。从拉曼和吸收光谱中研究了玻璃的结构特性，并证明了此玻璃中存在Ce3+离子。这种瞬态光栅起因于光克尔效应，并通过Ce3+离子中1S0?1F3电子能级跃迁形成的激发态粒子数光栅而改善，一级衍射信号的转换效率可达到11%。这些实验结果显示了掺杂CeO₂的75TeO₂-25Nb₂O₅-5ZnO飞玻璃在全转换开关中具有广泛应用。     

Polarization properties of SC generated in CaF2

Polarization of SC generated by 80 fs pulses of Ti:Sapphire laser strongly depends on the orientation of CaF₂ plate with respect to the plane of polarization of the pump light. Intensity modulation of the broad blue-shifted wing of SC against crystal rotation for the polarization parallel and orthogonal to the polarization of the pump beam is observed with CaF₂ and Sapphire. Observed modulation is due to evolution of the polarization state along the propagation distance in crystal.     

Further study of continuous-wave CO flame chemical laser of the CS2/O2/N2O type

This report describes an experimental examination of the output characteristics of the continuous-wave (cw) carbon monoxide flame chemical laser (FCL) of the CS₂/O₂/N₂O type in case of small CS₂/O₂ reactants ratios (tipically CS₂/O₂≦1/10). A linear burner which gives a homogeneous and stable flame was used during the experimental study. The measurements of temperature distribution in CS₂/O₂ as well as CS₂/O₂/N₂O flames show maximum temperatures of 1040 and 890 K, respectively. The addition of nitrous oxide (N₂O) leads to dramatically enhanced output laser power caused primarily by V?V transfer processes. A chemical efficiency, based on the reaction O+CS→CO^*+S, of 3% was achieved. The spectral composition of the CO FCL of the CS₂/O₂/N₂O type shows lasing in the region from 5.130 to 5.586 μm. Experimental results were obtained with a nondispersive optical cavity.     

Photochemical sensitization and magnetic field effect on ultrafine particle formation from a gaseous mixture of glyoxal and carbon disulphide

Under light irradiation at 435.8 nm with a medium-pressure mercury lamp, a gaseous mixture of glyoxal (GLY) and carbon disulphide (CS₂) produced sedimentary aerosol particles at the initial stage of light irradiation. The nucleation process of the aerosol particles was investigated by measuring He-Ne laser light intensity scattered by the aerosol particles as formed under light irradiation at 435.8 nm. From the dependence of the scattered light intensity on the partial pressure of GLY, it was found that electronically excited GLY in the n-π* state initiated chemical reactions with CS₂ leading to nucleation of the aerosol particles. An external magnetic field effect on the nucleation process was measured for a gaseous mixture of GLY and CS₂. With the application of a magnetic field of 5.1 kG, the nucleation reaction was accelerated and the convection of the gaseous mixture was changed. The magnetic field effect on the gaseous mixture is briefly discussed in comparison with the results obtained from a gaseous mixture of GLY and acrolein recently reported by us.     

Generation of 12 fs deep-ultraviolet pulses by four-wave mixing through filamentation in neon gas

Generation of deep-ultraviolet femtosecond pulses by four-wave mixing through filamentation in neon gas was demonstrated. Fundamental (omega) and second-harmonic (2omega) pulses of 25 fs Ti:sapphire amplifier output were focused into neon gas, and 20 microJ pulses with the center wavelength of 260 nm were produced by a four-wave mixing process, 2omega+2omega-omega?3omega through an ~15 cm filament. Additionally, pulses with an energy of 2 microJ at 200 nm were generated, probably by a cascaded process, 3omega+2omega-omega?4omega. The 260 nm pulses were compressed by a grating-based compressor and characterized by a dispersion-free transient grating frequency-resolved optical gating. The estimated pulse width was 12 fs.     

Photoinduced electron transfer of Rhodamine 6G/N,N-diethylaniline revealed by multiplex transient grating and transient absorption spectroscopies

The dynamics and spectroscopic characteristics of the ultrafast photoinduced electron transfer (ET) of Rhodamine 6G (Rh6G⁺) in N,N-diethylaniline (DEA) were studied using femtosecond time-resolved multiplex transient grating and transient absorption spectroscopies. The ultrafast photoinduced forward ET from DEA to the Rh6G⁺* cation radical excited state has a time constant of τ _FET = 219–318 fs. The much slower backward ET from the neutral radical Rh6G^· to DEA⁺ with a time constant of τ _BET = 22.76–42.31 ps occurs in the inverted region. Intramolecular vibrational relaxation of the excited state takes place in τ _IVR = 2.18–6.91 ps.     

The effect of S-functionalized and vacancies on V2C MXenes as anode materials for Na-ion and Li-ion batteries

The electrochemical properties of V₂C and V₂CT₂ (T = O, S) MXenes with and without vacancy as anode materials for Na-ion and Li-ion batteries, have been studied using first-principles calculation. The present results indicate that the adsorption strength of Li-ion and Na-ion on V₂CS₂ are less than that of O-functionalized, together with a lower diffusion barrier. Simultaneously, V₂CS₂ monolayer exhibits lower open-circuit voltage (OCV) values of 0.72 and 0.49 V for Li- and Na-ion, respectively. Interestingly, the presence of atomic vanadium vacancy on V₂CS₂ monolayer exerts more prominent effects on enhancing adsorption strength than that of carbon vacancy for Li-ion and Na-ion, but with an exception for the diffusion of Li-ion and Na-ion on V₂CS₂ monolayer. The finding suggests that the V₂CS₂ monolayer is expected to be a potential candidate as anode material for Li-ion and Na-ion battery due to its lower open-circuit voltages and diffusion barriers.     

A comprehensive study of (CH3)2CHOC(S)SC(O)OCH3 using matrix isolation technique,X‐ray analysis,spectroscopic studies and theoretical calculations

Potassium isopropyl xanthate, (CH₃)₂CHOC(S)SK, reacts with methyl chloroformiate ClC(O)OCH₃ to yield (methoxycarbonyl) (2‐propoxythiocarbonyl) sulfide, (CH₃)₂CHOC(S)SC(O)OCH₃. This novel xanthogen formate was characterized by ¹H and ¹³C{¹H} NMR spectroscopy, mass spectrometry and IR and Raman spectroscopy. The structure of a single crystal of (CH₃)₂CHOC(S)SC(O)OCH₃ was determined by X‐ray diffraction analysis at 173 K. The conformational properties have been studied by liquid IR and Raman spectroscopy, matrix isolation spectroscopy together with photochemical studies and quantum chemical calculations (HF and B3LYP methods with the 6‐31+G* basis set). The analysis of the IR spectrum of liquid (CH₃)₂CHOC(S)SC(O)OCH₃ suggests the presence of two conformers in equilibrium at room temperature. However, in the photochemical matrix study, an equilibrium of three conformers was detected. These forms were further characterized by theoretical calculations. Different photolysis products, such as CH₃OC(O)SCH(CH₃)₂, OCS, CO, CO₂ and CS₂, were identified by matrix spectroscopy. The IR absorptions of CH₃OC(O)SCH(CH₃)₂, for which literature data are scarce, were analysed in the light of the results of appropriate theoretical calculations. Copyright © 2009 John Wiley & Sons, Ltd.