Structural and solvent dependence of superexciplex

In this paper, we show that a few coumarin dye solutions exhibit dual amplified spontaneous emission (ASE) spectra under pulsed laser excitation, though all these solutions exhibit only one fluorescence band under steady-state conditions. The anomalous band, appearing only in ASE spectra, had been attributed to the superexciplex--a new molecular species. This is made of two excited molecules and is obtainable only under pulsed laser excitation. This complex is different from the well known excimer or exciplex, wherein only one atom or molecule is in the excited state. The superexciplex is possible with the two polar excited molecules coming together to form an excited state association, with the solvent acting as some sort of bridge. With very polar dye molecules, such an association is possible even with the inert benzene acting as a bridge; otherwise solvents like ethyl acetate, with an oxygen atom, is necessary for the linkage.     

Multiphoton ionization of molecules in selectively excited rovibrational states

Reported are observations of multiphoton ionization of a molecule (NO) due to sequential excitation by a tunable infrared laser and a tunable dye laser. These double-resonance experiments yield multiphoton ionization spectra of specific rotational levels, selectively populated by direct IR absorption. This technique simplifies complex multiphoton ionization spectra and offers a means of sensitively and selectively detecting IR absorption of molecules.     

Fluorescence resonance energy transfer in a novel two-photon absorbing system

A novel fluorescence resonance energy transfer (FRET) system containing a two-photon absorbing dye and a nile red chromophore has been synthesized. Upon two-photon excitation by laser at 815 nm this molecule displays efficient energy transfer from the two-photon absorbing dye to the nile red moiety, with an 8-fold increase in emission compared to the model compound. Similarly, single-photon excitation of the two-photon absorbing moiety at 405 nm results in >99% energy-transfer efficiency, along with a 3.4-fold increase in nile red emission compared to direct excitation of the nile red chromophore at 540 nm. This system provides an effective way to use IR radiation to excite molecules that, by themselves, have little or no two-photon absorption.     

Photodegradation of Luminescence in SiO2 : Rh B Gels Exposed to YAG : Nd Laser Pulses

Silicate gels doped with organic dyes have been proposed as solid-state tunable lasers. Photobleaching of the dye under laser excitation is an important phenomenon in this application. The optical absorption and luminescence of SiO2 silica gels doped with Rhodamine B exposed to the second harmonic pulses of a YAG : Nd laser have been studied. In addition to the characteristic exponential decay with the number of pulses, overlapping oscillations in the intensity were observed. This behavior is explained in terms of a long lived metastable electronic excited state of the dye molecules.     

FT-Raman studies of langmuir-blodgett monolayer components containing absorbing chromophores

Structural studies of Langmuir-Blodgett monolayers and multilayers have revealed that both the hydrophilic and the hydrophobic parts of an amphiphilic molecule can influence the exent of 2-dimensional packing which occurs within a film. In particular, dye chromophores to which are appended long hydrocarbon tails will usually form films dominated by the interaction of the chromophores unless a small amount of hydrocarbon liquid is added. In this case the packing will be dominated by the intermolecular interaction of the hydrocarbon tails. FT-Raman studies of these amphiphilic molecules provides information about both parts of the molecule without resonance enhancement since the laser wavelength used for excitation is far removed from any absorption maxima of the dye chromophore. Specific examples of thiocyanine and merocyanine dyes will be discussed.     

Optical imaging of excited-state tautomerization in single molecules

Tautomerism process of single fluorescent molecules was studied by means of confocal microscopy in combination with azimuthally or radially polarized laser beams. During a tautomerism process the transition dipole moment (TDM) of a molecule changes its orientation which can be visualized by the fluorescence excitation image of the molecule. We present experimental and theoretical studies of two porphyrazine-type molecules and one type of porphyrin molecule: a symmetrically substituted metal-free phthalocyanine and porphyrin, and nonsymmetrically substituted porphyrazine. In the case of phthalocyanine the fluorescence excitation patterns show that the angle between the transition dipole moments of the two tautomeric forms is near 90°, in agreement with quantum chemical calculations. For porphyrazine we find that the orientation change of the TDM is less than 60° or larger than 120°, as theoretically predicted. Most of the porphyrin molecules show no photoinduced tautomerization, while for 7% of the total number of investigated molecules we observed excitation patterns of two different trans forms of the same single molecule. We demonstrate for the first time that a molecule, undergoing a tautomerism process stays in one tautomeric trans conformation during a time comparable with the acquisition time of one excitation pattern. This allowed us to visualize the existence of each of the two trans forms of one single porphyrin molecule, as well as the sudden switching between these tautomers.     

Energy transfer and fluorescence quenching in complexes of polymethine dyes with human serum albumin

Electronic excitation energy transfer (EET) between molecules of polymethine dyes bound to human serum albumin (HSA) has been established and studied by absorption and fluorescence spectroscopy as well as by fluorescence decay measurements. In this system, excitation of the donor dye molecule leads to fluorescence of the acceptor dye molecule, both bound to HSA, with donor fluorescence quenching by the acceptor. The short distance between the donor and the acceptor (25-28 A) revealed from the Forster model of EET as well as some spectroscopic data show that both molecules are probably located in the same binding domain of HSA. The role of HSA is to bring donor and acceptor molecules together to a distance adequate to achieve EET as well as to increase the donor and acceptor fluorescence quantum yields. Efficient quenching of the intrinsic HSA fluorescence by some polymethine dyes (oxonols) is observed. The experimental results fit well a model for the formation of a weakly fluorescent dye-HSA complex; the quencher in this complex should be located in the immediate vicinity of the HSA fluorophore group (Trp(214)).     

Infrared multiphoton excitation of small molecules

The collisionless infrared excitation by short CO₂ laser pulses of the molecules SO₂, OCS, NO₂, NH₃ and DN₃ is compared with that of larger molecules. The average number of photons absorbed per molecule and the fraction of molecules dissociated depends predominantly on the laser intensity, while for larger molecules with higher densities of vibrational states the excitation is primarily determined by the laser fluence.     

甲胺分子多光子电离质谱研究

胜多光子电离飞行时间质谱法，利用可调谐脉冲激光器，测得了甲胺分子在不同激光波长和激光功率下的多光子电离和解离产物。母体离子ＣＨ３ＮＨ＾＋２的离解速常数随激光发波长的增大而减小。     

Concentration-dependent energy transfer studies in ternary dye mixture of Stilbene-420, Coumarin-540 and Nile Blue

The energy transfer studies in the case of ternary dye mixture [Stilbene-420 (donor)+Coumarin-540 (intermediator)+Nile Blue (acceptor)] have been done and discussed through optical gain characteristics at various acceptor concentrations under nitrogen laser excitation. The concentration of the other two dyes were kept constant. It is observed that the concentration of the acceptor dye plays a very critical role in energy transfer dye laser (ETDL) as small change in its concentration varies the intensity of the laser output in the red region by large amount. Also, the highest laser output in the red region is obtained when the concentration of the acceptor dye is slightly higher than that of the intermediator dye. The present studies are helpful in deciding the optimum concentration of the acceptor dye to be used in ternary dye mixture for maximum gain and tuning range. The ternary dye mixture under study provides an ETDL tuning range up to 700 nm.     

Mesostructured materials for optical applications: from low-k dielectrics to sensors and lasers

Recent advances on the use of mesoporous and mesostructured materials for electronic and optical applications are reported. The focus is on materials which are processed by block-copolymer templating of silica under weakly acidic conditions and by employing dip- and spin-coating as well as soft lithographic methods to bring them into a well-defined macroscopic shape. Several chemical strategies allow the mesostructure architecture to be used for electronic/optical applications: Removal of the block-copolymers results in highly porous, mechanically and thermally robust materials which are promising candidates for low dielectric constant materials. Since the pores are easily accessible, these structures are also ideal hosts for optical sensors, when suitable are incorporated during synthesis. For example, a fast response optical pH sensor was implemented on this principle. As-synthesized mesostructured silica/block-copolymer composites, on the other hand, are excellently suited as host systems for laser dyes and photochromic molecules. Laser dyes like rhodamine 6G can be incorporated during synthesis in high concentrations with reduced dimerization. This leads to very-low-threshold laser materials which also show a good photostability of the occluded dye. In the case of photochromic molecules, the inorganic-organic nanoseparation enables a fast switching between the colorless and colored form of a spirooxazine molecule, attributed to a partitioning of the dye between the block-copolymer chains. The spectroscopic properties of these dye-doped nanocomposite materials suggest a silica/block-copolymer/dye co-assembly process, whereby the block-copolymers help to highly disperse the organic dye molecules.     

Local Extraction and Condensation under a Microscope Using the Optically Controlled Phase Separation of a Thermoresponsive Polymer

In‐situ extraction and condensation of various dyes were carried out in a phase‐separation region of a thermoresponsive polymer aqueous solution generated by near infrared (NIR) laser heating under a microscope. The NIR laser irradiation was directed at a chromium line deposited on a glass substrate, thereby causing local heating of the solution due to the photothermal effect. A phase‐separation region was formed by dehydration of the thermoresponsive polymer followed by ejection of water outside of the phase‐separation region. When various dyes were included in the solution, some dye molecules were extracted into the phase‐separation region, where they condensed. In the case of poly(N‐isopropylacrylamide) (PNIPAM, 10 wt % in an aqueous solution) as the thermoresponsive polymer and crystal violet (CV) as the dye (0.1 mM ), CV condensed by about 25 times. It was found that one of the necessary conditions for the extraction/condensation is the hydrophobicity of the dye molecule; however, the dominant cause for accumulating inside the PNIPAM chain is the molecular interaction between the amide group in the side chain of PNIPAM and the functional groups such as carbonyl or amino groups in the dye molecules.     

Absorption and fluorescence spectroscopy of rhodamine 6G in titanium dioxide nanocomposites

A comparison has been made between the spectroscopic properties of the laser dye rhodamine 6G (R6G) in mesostructured titanium dioxide (TiO(2)) and in ethanol. Steady-state excitation and emission techniques have been used to probe the dye-matrix interactions. We show that the TiO(2)-nanocomposite studied is a good host for R6G, as it allows high dye concentrations, while keeping dye molecules isolated, and preventing aggregation. Our findings have important implications in the context of solid state dye-lasers and microphotonic device applications.     

SnO2/SiO2 and Sn/Sb-oxide/SiO2 gel-derived composites. Part 1: Structural evolution from a Mössbauer study

The lasing photostability of the red perylimide dye (RPD) in various solid matrices was measured under frequency-doubled Nd:YAG laser excitation. The RPD: composite glass laser intensity decayed to 50% of its initial value after approximately 20,000 pump pulses of 13 mJ/pulse. The output of RPD:ormosil glass and RPD:PMMA glass lasers decayed to 50% of their initial value after 1,200 and 1,000 pump pulses of the same energy, respectively. For rhodamine-6G:silica-gel and rhodamine-6G:ormosil glass lasers, the 50% decay occurred already after 1,000 and 300 pulses, respectively. The decay was non-exponential, suggesting that the dye bleaching was not a single-photon process. The average laser output decay rates increased linearly with the pump energy. Singlet-singlet excited state absorption of the RPD dye in the solid matrices was also measured between 550 and 730 nm. At ～600 nm the cross section was ～2×10^?16 cm²/molecule. The excited-state absorption competes with the lasing, and is a main factor that limits the laser efficiency.     

Hybrid materials for solid-state dye laser applications

The quest for a solid-state tunable dye laser can be satisfied by sol-gel prepared organic-inorganic hybrids. A photostability study of porous silica-Rhodamine 6G hybrids prepared via a sol-gel method is presented. The dye molecules can be incorporated into the silica matrix by forming weak or covalent bonds (hybrids of classes I and II, respectively). New class II samples and traditional class I materials prepared by the pre-doping method were synthesized. Samples were characterized by photoluminescence measurements to compare the emission properties and the photostability of the samples. The decay of the fluorescence signal as the cumulative excitation energy increases is reported and interpreted by hypothesizing that the dye molecules can be hosted in different surroundings within the porous glass matrix. The reported photoluminescence and photobleaching features indicate the class II samples as good candidates for solid-state dye lasers.     

Pre-resonance Raman intensity studies of TCNQ and TCNQ−

Pre-resonance Raman spectra have been obtained for TCNQ and LiTCNQ in acetonitrile solution using an Ar⁺—Kr⁺ laser and a tunable rhodamine 6G dye laser. Using the theory of Albrecht and Hutley, we have calculated frequency factors for the intensity variations for several symmetric vibrational modes of each molecule. The observed spectra for TCNQ and LiTCNQ with violet, blue, and green excitation give evidence for B-type resonance enhancement due to vibronic mixing between at least two violet and ultraviolet transitions. The Raman spectra for LiTCNQ with yellow, orange, and red excitation show A-type enhancement due to a single electronic excitation in the near infrared.     

Unprecedented laser action from energy transfer in multichromophoric BODIPY cassettes

A cassette molecule, featuring direct integration of two donor BODIPY units to one acceptor BODIPY unit, was conveniently developed as the first highly "through-bond energy transfer" (TBET) laser dye. This multicolor absorbing dye exhibited highly efficient and photostable laser action under drastic pumping conditions.     

Two-laser studies of E → V energy transfer reactions involving CO and electronically excited I2, ICl and NO2

The relaxation of electronically excited I₂, ICl and NO₂ by CO has been investigated using a dye laser for electronic excitation (in the 590 nm region) and a cw CO laser for measuring the extent of CO product vibrational excitation. The CO molecules formed in these quenching reactions were found to carry very small fractions of electronic energies, in sharp contrast to the results observed in other E → V transfer reactions involving atomic species which carry comparable amounts of electronic energies.     

Effect of the excitation source on the quantum-yield measurements of rhodamine B laser dye studied using thermal-lens technique.

A dual-beam transient thermal-lens technique was employed for the determination of absolute fluorescence quantum-yield measurements of Rhodamine B laser dye in different solvents. We investigated the effect of excitation on the absolute fluorescence quantum yield of Rhodamine B. 514 nm radiation from an argon ion laser was used as a cw excitation source and 532 nm pulses from a Q-switched Nd:YAG laser were used as a pulsed excitation source. The fluorescence quantum-yield values were found to be strongly influenced by environmental effects as well as the transient nature of the excitation beam. Our results also indicate that parameters, like the concentration of the dye solution, aggregate formation and excited state absorption, affect the absolute values of the fluorescence yield significantly.