Characterization of ammonia two-photon laser-induced fluorescence for gas-phase diagnostics

Two-photon laser-induced fluorescence (LIF) of ammonia (NH₃) with excitation of the C′-X transition at 304.8 nm and fluorescence detection in the 565 nm C′-A band has been investigated, targeting combustion diagnostics. The impact of laser irradiance, temperature, and pressure has been studied, and simulation of NH₃-spectra, fitted to experimental data, facilitated interpretation of the results. The LIF-signal showed quadratic dependence on laser irradiance up to 2 GW/cm². Stimulated emission, resulting in loss of excited molecules, is induced above 10 GW/cm², i.e., above irradiances attainable for LIF imaging. Maximum LIF-signal was obtained for excitation at the 304.8 nm bandhead; however, lower temperature sensitivity over the range 400–700 K can be obtained probing lines around 304.9 nm. A decrease in fluorescence signal was observed with pressure up to 5 bar absolute and attributed to collisional quenching. A detection limit of 800 ppm, at signal-to-noise ratio 1.5, was identified for single-shot LIF imaging over an area of centimeter scale, whereas for single-point measurements, the technique shows potential for sub-ppm detection. Moreover, high-quality NH₃-imaging has been achieved in laminar and turbulent premixed flames. Altogether, two-photon fluorescence provides a useful tool for imaging NH₃-detection in combustion diagnostics.     

9,10-Anthracene-centered oligo(p-phenyleneethynylene)s with end-capping didecylamines exhibiting enhanced two-photon fluorescence action cross-section

This study reports the synthesis and the two-photon absorption (TPA) properties of a series of 9,10-anthracene-centred oligo(p-phenyleneethynylene)s with end-capping didecylamine. The results show that both the maximal TPA cross-sections (δ_max) and the fluorescence quantum yields (Φ) of the oligomers increase with the extension of phenylethynyl bridges. Interestingly, the Φδ_max per repeating unit to is obviously enhanced by extending linearly conjugation size of the oligomers. Moreover, these oligomers all show the maximal two-photon absorption cross-sections at 800 nm and emit strong green to yellowish-green two-photon excited fluorescence. These materials may find applications in which two-photon excited fluorescence and photo-induced electron transfer are utilized.     

Luminescent Fluorene-Based Bis-Pyrazolyl Aniline Ligand for Aluminum Detection

The design, synthesis, and photophysical properties of a new fluorene-based fluorescent chemosensor, 4-((E)-2-(2-(benzo[d]thiazol-2-yl)-9,9-diethyl-9H-fluoren-7-yl)vinyl)-N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzenamine (AXF-Al), is described for the detection of Al³⁺. AXF-Al exhibited absorption at 382 nm and strong fluorescence emission at 542 nm (fluorescence quantum yield, Φ _F, of 0.80). The capture of Al³⁺ by the pyrazolyl aniline receptor resulted in nominal change in the linear absorption (372 nm) but a large hypsochromic shift of 161 nm in the fluorescence spectrum (542 to 433 nm, Φ _F?=?0.88), from which Al³⁺ was detected both ratiometrically and colorimetrically. The addition of other metal ions, namely Mg²⁺, Ca²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg ²⁺ and Pb²⁺, produced only minimal changes in the optical properties of this probe. The emission band of this probe was also accessed by two-photon excitation in the near-IR, as two-photon absorption (2PA) is important for potential applications in two-photon fluorescence microscopy (2PFM) imaging. The 2PA cross section of the free fluorenyl ligand AXF-Al was 220 GM at 810 nm and 235 GM at 810 nm for the Al-ligand complex, practically useful properties for 2PFM.     

Fluorescence Anisotropy of Tyrosinate Anion Using One-, Two- and Three-Photon Excitation

We examined the emission spectra and steady-state anisotropy of tyrosinate anion fluorescence with one-photon (250–310 nm), two-photon (570–620 nm) and three-photon (750–930 nm) excitation. Similar emission spectra of the neutral (pH 7.2) and anionic (pH 13) forms of N-acetyl-L-tyrosinamide (NATyrA) (pK_a 10.6) were observed for all modes of excitation, with the maxima at 302 and 352 nm, respectively. Two-photon excitation (2PE) and three-photon excitation (3PE) spectra of the anionic form were the same as that for one-photon excitation (1PE). In contrast, 2PE spectrum from the neutral form showed ~30-nm shift to shorter wavelengths relative to 1PE spectrum (λ_max 275 nm) at two-photon energy (550 nm), the latter being overlapped with 3PE spectrum, both at two-photon energy (550 nm). Two-photon cross-sections for NATyrA anion at 565–580 nm were 10 % of that for N-acetyl-L-tryptophanamide (NATrpA), and increased to 90 % at 610 nm, while for the neutral form of NATyrA decreased from 2 % of that for NATrpA at 570 nm to near zero at 585 nm. Surprisingly, the fundamental anisotropy of NATyrA anion in vitrified solution at ?60 °C was ~0.05 for 2PE at 610 nm as compared to near 0.3 for 1PE at 305 nm, and wavelength-dependence appears to be a basic feature of its anisotropy. In contrast, the 3PE anisotropy at 900 nm was about 0.5, and 3PE and 1PE anisotropy values appear to be related by the cos⁶ θ to cos² θ photoselection factor (approx. 10/6) independently of excitation wavelength. Attention is drawn to the possible effect of tyrosinate anions in proteins on their multi-photon induced fluorescence emission and excitation spectra as well as excitation anisotropy spectra.     

Strong two-photon-induced fluorescence from a highly soluble polythiophene

Two-photon-induced fluorescence from a soluble polythiophene containing urethane side groups has been investigated using femto-second laser pulses at 800 nm. Strong two-photon fluorescence was measured in polymer solution. The quadratic dependence of the fluorescence on the excitation laser intensity confirmed the two-photon process. The measured two-photon absorption cross-section is larger as compared to those of other reported polythiophenes. This polymer can be readily hydrolyzed to yield a water soluble polythiophene which could be useful in biological imaging.     

以萘为π-中心的双芪类衍生物双光子上转换荧光性能研究

研究了2个新的双光子上转换荧光分子—1,4-双-(9-乙基咔唑基)萘(简称为BECVN)和1,4-双-(4’-N,N-二甲氨基苯乙烯基)萘(简称为BMABN)的单光子、双光子光谱性质。在～375 nm Xe灯光源激发下,两样品的DMF溶液发出很强的蓝、绿色荧光(峰位492～541 nm),视感效果非常明显。BMABN分子的线性吸收/发射光谱的峰位与BECVN分子相比,均发生红移;相对荧光量子产率(Φ_f)比BECVN降低了7.4倍。在飞秒钛宝石激光器泵浦下(760 nm),两样品的DMF溶液发出强的双光子上转换荧光发射,峰位与单光子荧光峰位相比发生红移(500～556 nm)。BMABN的双光子荧光强度和双光子吸收截面分别是BECVN的3倍和30.4倍。     

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-photon excitation of atomic oxygen in a flame

Atomic oxygen has been detected in a lean acetylene/oxygen flame using the 2p⁴³P₂-2p³3p³P two-photon transition at 226 nm and fluorescence detection at 845 nm.     

Photodynamics of intramolecular proton transfer in polar and nonpolar biflavonoid solutions

Using methods of steady state luminescence and femtosecond spectroscopy, we have studied the mechanism of intramolecular proton transfer in synthesized 3,7-dihydroxy-2,8-di(4-methoxyphenyl)-4H,6H-pyrano[3,2-g]chromen-4,6-dion in polar and nonpolar solutions, films, and polycrystals at 293 and 77 K. In an excited singlet state, intramolecular proton transfer occurs in two stages. At the first stage, a tautomer with one transferred proton (OTP tautomer) is formed from the Franck-Condon state within ??₁ = 0.6 ps. At the second stage, the second proton is transferred within ??₂ = 3.1 ps and a tautomer with two transferred protons (TTP tautomer) is formed, which fluoresces in toluene at 293 K with a high quantum yield, ?? _f = 0.66, and the fluorescence spectrum of which is characterized by a large Stokes shift, 9900 cm^?1. At 293 K, polar solvents (dimethylformamide, dimethyl sulfoxide, ethanol, etc.) solvate the BFV molecule in the ground state, while, in the excited state, an OTP tautomer is mainly formed. In polar ethanol at 77 K, a dual fluorescence spectrum is observed, which is caused by the fluorescence emission of polysolvates with ?? _max ^f = 460 nm and TTP phototautomers at ?? _max ^f = 610 nm.     

Growth, spectroscopic characteristics and laser potential of Yb3+:Ca3La2(BO3)4 crystal

Crystal of Yb³⁺-doped Ca₃La₂(BO₃)₄ has been grown by the Czochralski technique. The room temperature absorption and fluorescence spectra of the crystal have been investigated. The result showed that this crystal exhibits broad absorption and emission with the FWHM of 11 nm at 978 nm and 66 nm FWHM at 1025 nm, respectively. The stimulated emission cross-section of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg method, respectively. The room temperature fluorescence decay curves of ² F _5/2 manifold of Yb³⁺ ions were recorded for both crystal and powder samples. The effect of radiation tapping on the spectroscopic properties is discussed. The result that the lifetime of the powder sample is shorter than that of the bulk sample demonstrates the existence of radiation trapping effect. The laser potentiality was also evaluated and the results show that this crystal is a good candidate for tunable and ultrashort pulse lasers.     

Synthesis of TiO2 nanoparticles and spectroscopic upconversion luminescence of Nd3+-doped TiO2–SiO2 composite glass

Nd³⁺-doped TiO₂–SiO₂ composites were prepared by sol–gel method. Optical properties such as radiative life-time (τ), stimulated emission cross-section (σ_p) and branching ratio (β) were calculated using Judd–Ofelt theory. Violet to blue upconversion emissions at 380 nm (⁴D_3/2→⁴I_11/2), 399 nm (²P_3/2→⁴I_11/2), 420 nm (²D_5/2→⁴I_9/2) and 452 nm (²P_3/2→⁴I_13/2) were obtained under 578 nm xenon-lamp excitation. The choice of 578 nm is justified by the absorption spectra of the same samples, which shows a strong absorption peak at 578 nm. This 578 nm excitation pump produces upconversion in Nd³⁺ by a sequential two-photon absorption process.     

Structural and electrochemical properties of LiNi1/3Co1/3Mn1/3O2 material prepared by a two-step synthesis via oxalate precursor

LiNi_1/3Co_1/3Mn_1/3O₂ (LNMCO) powders were formed by a two-step synthesis including preparation of an oxalate precursor by ??chimie douce?? followed by a solid-state reaction with lithium hydroxide. The product was characterized by TG-DTA, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), Raman spectroscopy, electron spin resonance (ESR), and SQUID magnetometry. XRD data revealed well-crystallized layered LNMCO with ??-NaFeO₂-type structure (R-3?m space group). Morphology studied by SEM and TEM shows submicronic particles of 400?C800?nm with a tendency to agglomerate. The local structure investigated by vibrational spectroscopy (FTIR, Raman), ESR, and SQUID measurements confirms the well-crystallized lattice with a cation disorder of 2.6% Ni²⁺ ions in Li(3b) sites. Electrochemical tests were carried out in the potential range 2.5?C4.5?V vs. lithium metal on samples heated at 900?°C for 12?h. Initial discharge capacity is 154 mAh/g at C/5, while a capacity of 82 mAh/g is still delivered at 10 C by the two-step synthesized LiNi_1/3Co_1/3Mn_1/3O₂ as cathode material.     

Enhanced four-wave mixing in mercury isotopes, prepared by stark-chirped rapid adiabatic passage

We demonstrate significant enhancement of four-wave mixing in coherently driven mercury isotopes to generate vacuum-ultraviolet radiation at 125 nm. The enhancement is accomplished by preparation of the mercury atoms in a state of maximum coherence, i.e. maximum nonlinear-optical polarization, driven by Stark-chirped rapid adiabatic passage (SCRAP). In this technique, a pump laser at 313 nm excites the two-photon transition between the ground state 6s²¹S₀ and the target state 7s ¹S₀ in mercury. A strong, off-resonant radiation field at 1064 nm generates dynamic Stark shifts. These Stark shifts serve to induce a rapid adiabatic passage process on the two-photon transition. During the process a coherent superposition of the two states is established, which enhances the nonlinear-optical polarization in the medium to the maximum possible value. The maximum coherence permits efficient four-wave mixing of a pump laser and an additional probe laser at 626 nm. The efficiency is further enhanced, as the SCRAP process allows to stimulate the complete set of different mercury isotopes to participate in the frequency conversion process. This enlarges the effective atomic density of the medium. Thus, we observe the generation of vacuum-ultraviolet radiation at 125 nm enhanced by more than one order of magnitude with respect to conventional frequency conversion. Parallel to the frequency conversion process, we monitored the evolution of the population in the medium by laser-induced fluorescence. These data demonstrate efficient coherent population transfer by SCRAP.     

Two-photon exchange in p⊆)p→ℓ+ℓ−X and a comparison with QCD

A thorough study of lepton-pair production from two-photon annihilation in p?)p collisions is presented. The differential cross section is calculated over a large range of energies (27?√s?800 GeV as a function of the dilepton mass M as well as the dilepton transverse momentum Q_T and the Feynman variable x_F. No kinematical approximations (such as the equivalent photon approximation) are made. For Q_T ≈ 0 the two-photon mechanism represents an important fraction of the pp→e⁺e^?X cross section already at ISR energies, whereas at ISABELLE energies it dramatically dominates in the interval 0?Q_T?1 GeV. At ISR energies these conclusions follow from a direct comparison of the two-photon contribution with pp→e⁺e^?X data. For the ISABELLE energy range the expected O(α_s) QCD contribution to pp→?⁺?^?X, corrected for soft gluon radiation to all orders (in leading bilogarithmic approximation), was taken as a reference. At larger Q_T and ISR energies the γγ contribution is negligible, whereas at √s = 800 GeV γγ/QCD? 10–20% almost everywhere. Furthermore, two-photon candidate events from the ISR are shown to be in reasonable agreement with theory. A decomposition of the γγ cross section into contributions from both proton vertices being elastic, inelastic and of mixed configuration is given. The results provide important clues for a future isolation of the two-photon mechanism.     

Thermal stability and spectroscopic properties of Er-doped lead fluorogermanate glasses

The thermal characterization and spectroscopic properties of Er³⁺-doped 0.6GeO₂-(0.4-x)PbO-xPbF₂ glasses were investigated experimentally. With the replacement of PbO by PbF₂ the thermal stability of glasses is improved and the infrared fluorescence intensity at 1530 nm is increased. The Judd-Ofelt intensity parameters, radiative transition rates, and fluorescence lifetimes of the excited ⁴I_13/2 level of Er³⁺ ions were calculated from Judd-Ofelt theory. The asymmetric ligand field around Er³⁺ ions resulted from the incorporation of PbF₂ into germanate glasses, broadens the infrared emission spectra at 1530 nm. Upconversion luminescence in the investigated glasses was observed at room temperature under the excitation of 976 nm laser diode. The glass 0.6GeO₂-0.3PbO-0.1PbF₂ exhibits the maximum upconversion emission intensity, while no frequency upconversion luminescence was observed in the 0.6GeO₂-0.4PbO glass. The quadratic dependence of the green and red emissions on excitation power indicates that two-photon absorption contributes to the visible emission under the 976-nm excitation.     

Absorption and emission spectroscopic characterisation of F<Subscript>3</Subscript><Superscript>-</Superscript> colour centers in a LiF crystal

For a LiF crystal containing F₃ (R₁, R₂), F₂, F₃ ⁺, F₄ (N₁, N₂), F₃ ^-, and F₂ ^- colour centers the absorption and emission spectroscopic behaviour of the F₃ ^- centers is studied. The absorption cross-section spectrum and the number density of F₃ ^- centers are extracted from saturable absorption and transmission measurements. Additionally fluorescence quantum distribution measurements and fluorescence lifetime measurements are carried out to determine the stimulated emission cross-section spectrum and the fluorescence quantum yield of the F₃ ^- centers. Fluorescence excitation spectroscopy reveals the presence of an absorption band with its absorption peak around 700 nm (called R ₁ band) in addition to the ground-state to first excited-state F₃ ^- center absorption band centered at 800 nm (called R ₂). PACS 61.72.Ji; 78.40.Ha; 78.55.Fv     

Triplet-Triplet fluorescence of 9,10-dibromanthracene in hexane

The temperature dependence of the triplet-triplet fluorescence (TTF) spectrum of 9,10-dibromanthracene in hexane is studied in the near infrared region between 800 and 1050 nm in the temperature range from 200 to 320 K. The TTF spectrum exhibits two distinct bands at 842 and 949 nm at 293 K. Upon cooling from 293 to 200 K, the intensity of the 842-nm band decreases and that of the 949-nm band increases. The different behavior of the band intensities is explained by the overlap of the emission at 950 nm, which can be related to a photoproduct. The 842-nm band is assigned to the 0-0 T ₂(³ B _1g →T ₁(³ B _2u transition. The quantum yield of TTF at 293 K measured within the 842-nm band is 8.3×10^?7 (±20%)), and for emission in the region from 800 to 1050 nm it is equal to 1.4×10^?6 (after subtraction of the contribution from the S ₁→S ₀ singlet-singlet fluorescence). The effect of the intersystem crossing and internal conversion on the temperature dependence of TTF is discussed.     

Calculation of the 1s–2s two-photon excitation cross-section in atomic hydrogen

The two-photon excitation cross-section of atomic hydrogen is calculated using explicit summation over intermediate states within the framework of dipole approximation. The matrix element for two-photon excitation is transformed into finite sums, consisting of the product of a radial and angular part. Nine intermediate states are employed in the calculation of the transition matrix element. The two-photon excitation cross-section obtained for the transition 1s ²S_1/2–2s ²S_1/2in atomic hydrogen is a good agreement with the literature.     

Nonlinear optical properties of an azo-based dye irradiated by picosecond and nanosecond laser pulses

The nonlinear optical properties of an azo-based dye were investigated using Z-scan technique employing 38 ps pulses at 532 and 1064 nm, and 6 ns laser pulses at 532 nm. Large nonlinear absorption and nonlinear refraction were observed at both ps and ns 532 nm in the azoic dye. When excited at ps 1064 nm, this dye displayed a large two-photon absorption cross-section (σ₂=1810 GM). Meanwhile, the optical nonlinearity mechanism was discussed in terms of molecular structure, excitation wavelength, and pulse width.     

Optical detection of near infrared femtosecond laser-heating of Er-doped ZnO-Nb2O5-TeO2 glass by green up-conversion fluorescence of Er ions

The green up-conversion fluorescence of Er³⁺ ions doped in an nonlinear optical ZnO-Nb₂O₅-TeO₂ glass was observed by using 800 nm excitation from a regenerative femtosecond (fs) Ti:Sapphire laser. The detailed analysis on two fluorescence lines at 526 nm (²H_11/2-⁴I_15/2) and 548 nm (⁴S_3/2-⁴I_15/2) revealed the fs laser heating of the multi-component TeO₂-based glass, which was possibly due to its nonlinear absorption of the host glass via the imaginary part of the third-order optical susceptibility (χ⁽³⁾). The result was compared with that of a Er³⁺-doped aluminosilicate glass under the same irradiation condition. When the fs laser was irradiated to the multicomponent TeO₂-based glass in the power density of 150 TW/cm², the laser spot was heated up to ∼520 K, which however was still less than the glass transition temperature (T_g=688 K). This technique provides a useful sensing method of laser spot temperature even inside transparent materials.