One- and Two-Photon Fluorescence Anisotropy of Selected Fluorene Derivatives

The steady-state excitation anisotropy spectra of fluorene derivatives were measured in viscous solvents, under the one- and two-photon excitation, over a broad spectral range (UV–Visible). The orientation of their absorption transition moments for the first, S₀S₁, and second, S₀S₂, excited states were determined. It was shown experimentally that a decrease in the angle between S₀S₁and S₀S₂ transitions corresponded to an increased value of two-photon absorption (2PA) cross section for these molecules. Two-photon excitation anisotropy was nearly constant over the spectral region investigated (in contrast to one-photon excitation anisotropy spectra) and can be roughly explained by a simple model of 2PA based on the single intermediate state approximation. For comparison, the same trend in two-photon excitation anisotropy was observed for Rhodamine B inglycerol.     

All-Optical Half-Adder Using All-Optical XOR and AND Gates for Optical Generation of “Sum” and “Carry”

Abstract

In this article, a numerical simulation study using the symmetric planar three-core non-linear directional coupler, operating with a short light pulse (2 ps), for the implementation of an all-optical half-adder is presented. The half-adder is the key building block for many digital processing functions such as shift register, binary counter, and serial parallel data converters. Optical couplers are an important component for application in optical fiber telecommunication systems and all integrated optical circuits because of very high switching speeds (as high as the femto-second range). In this numerical simulation, the symmetric planar three-core non-linear directional coupler presents a planar symmetrical structure with three cores in a parallel equidistant arrangement, three logical inputs (CP, A, and B), and two output logic functions (C and S). The CP(ΔΦ) input is a control pulse with a phase difference ΔΦ = Δθπ (0 ≤ Δθ ≤ 2) between inputs A and B (logical inputs of the half-adder) and one amplitude discriminator circuit. The half-adder uses two output logic functions of Sum(S) and Carry(C), which can be demonstrated by using XOR and AND gates, respectively. For the half-adder, the phase [ΔΦMIN, ΔΦMAX] intervals are studied, allowing the operation of the device as a half-adder. For the selected range of CP(ΔΦ_BETTER), the extinction ratio was studied, the compression factors for both Sum(S) and Carry(C) outputs of the symmetric planar three-core non-linear directional coupler.     

The Phosphorescence Excitation Spectrum of Jet-Cooled Xanthione in the Region of the T1←S0 and S1←S0 Absorption Transitions

The ³A₂(nπ*)→¹A₁X (T₁→S₀) phosphorescence excitation spectrum of jet-cooled xanthione was investigated in the region 14 920-17 600 cm⁻¹. The structure observed is shown to be due to the T₁←S₀ absorption and an assignment in terms of the vibronic structure of that band is proposed. A previous assignment of the S₁←S₀ origin is considered in detail and the transition involved is shown to be most probably due to absorption of a vibronic triplet state T_1z,ν7. An alternative but tentative assignment of the S_1,0←S_0,0 transition is suggested. Comparison is made with previous spectroscopic and theoretical work on the molecule and its congeners, 4H-pyran-4-thione and 4H-1-benzopyran-4-thione.     

A thermometry technique based on atomic lineshapes using diode laser LIF in flames

We report on the development of a novel diode laser thermometry technique permitting temperature measurements in flames based on the fluorescence lineshapes of an atomic tracer species. The technique, which we term OLAF (one-line atomic fluorescence) requires only a single diode laser source for excitation, is simple to implement, and has excellent spatial resolution. Temperatures are deduced from the 5²P_1/2 → 6²S_1/2 transition of atomic indium, the lineshape of which is highly sensitive to temperature changes at typical flame conditions. A rigorous validation is performed in a reference flame with comparisons to measurements by CARS and by Na-line reversal, and to numerical simulations.     

Luminescence of Pr-doped LiCaAlF6 and LiSrAlF6 crystals

The spectral and kinetic parameters of LiCaAlF₆:Pr and LiSrAlF₆:Pr single crystals are studied at LHeT and room temperature (RT). Photon cascade emission (PCE), i.e., ¹S₀→¹I₆ and ³P₀→³H_j, ³F_j transitions after Pr³⁺ excitation via 4f²→4f 5d absorption results in the conversion of the vacuum ultraviolet photon to two visible photons. The excitation and photoemission spectra as well as decay times have been measured and compared with those for CaF₂:Pr and SrF₂:Pr crystals. X-ray luminescence was measured to study the emission origin from both ¹S₀ and ³P₀ states of Pr³⁺. An intense phosphorescence of LiSrAlF₆:Pr was observed in the visible range after X-irradiation at RT, contrary to LiCaAlF₆:Pr.     

Effect of annealing and Mn doping on the photoluminescence of strontium tartrate crystals

Strontium tartrate crystals (STC) were grown in gel using the single tube diffusion method. Powder XRD and FTIR spectroscopy were used for the characterization of the crystal. The optical band-gap (Eg) of STC is found to be 5.46 eV. Photoluminescence (PL) spectra of STC are recorded at different annealing temperature and concentration of dopant Mn. The spectral peaks (λ_em) of strontium tartrate photoluminor lie around 417, 440, 513 and 620 nm with excitation wavelength (λ_exc)=379 nm. The peaks at 417, 513 and 620 nm correspond to transitions ²P_1/2⁰→²S_1/2, ¹D⁰→³P⁰ and ¹S→³P⁰, respectively of Sr. The PL peak observed around 440 nm corresponds to the a⁴D_7/2→a⁶S_5/2 transition of Mn.     

High-contrast all-optical switching with Pt:ethynyl complex

We have theoretically analyzed all-optical switching in Pt:ethynyl complex based on nonlinear excited-state absorption. A detailed analysis for Pt:ethynyl complex has been presented based on rate equation approach. It is shown that a pulsed pump laser beam at 355 nm switches the transmission of a cw probe laser beam at 633 nm through a Pt:ethynyl sample. The effect of various parameters, such as pump pulse width, peak pumping intensity, normalized parameter , transition times of S₁→S₀ and S₁→T₁ states and lifetime of triplet state, on switching characteristics has been analyzed in detail. It has been shown that the probe beam can be completely switched off (i.e. 100% modulation) by a pulsed pump laser beam at 50 kW/cm². These results have been used to design all-optical NOT and the universal NOR and NAND logic gates with multiple pump laser pulses.     

Polarized fluorescence of β-carotene and related polyenes

The spectral and polarization characteristics of trans-isomers ofβ-carotene, lycopene, retinal, and 1,6-diphenylhexatriene (DPH) in solutions have been investigated by the methods of polarized fluorescence and semiempirical calculations of AM1 and RM3. The high and constant values of the degree of polarization P ∼0.46, closely coinciding with the limiting value P₀=0.5, according to the S₂→S₀-fluorescence and S₂←S₀-fluorescence excitation spectra ofβ-carotene and lycopene in n-hexane at room temperature and also high and coinciding according to the S₁→S₀-fluorescence and S₂←S₀-fluorescence excitation spectra for retinal in EPA at 77 K and DPH in a polyvinylbutyral film, point to the coincidence of the directions of absorption and emission oscillators. These oscillators are aligned along the major axis of the polyene molecule, and the longwave S₂←S₀-absorption band is formed only by one electronic¹B _u ⁺ ←¹A _g ⁻ -transition. The oscillators of shortwave S_a←S₀-absorption bands are aligned at an angle to the oscillators of the S₂←S₀-transitions, which is related to the distortions in the structure of molecules (β-carotene, lycopene) or, as in the case of DPH, to the influence of transitions localized on the orbitals of phenyl rings and polarized perpendicularly to the major axis of the molecule. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 69–74, January–February, 2000.     

Wave mixing and amplified spontaneous emission in pure potassium and mixed sodium-potassium vapors

We report observations of several wave-mixing and stimulated processes in pure potassium and mixed sodium-potassium vapors which are excited by a pulsed laser operating in the range 680–800 nm. When the laser is tuned to the potassium two-photon 4S6S transition, we observe stimulated emission on the various cascade transitions as well as four- and six-wave mixing. When the laser is tuned over the range 747 to 753 nm, which is well away from all atomic transitions, we observe strong forward and weak backward emission at the potassium 3D _3/24P _1/2 transition wavelength (1.17 m). However, this latter emission is only observed in the mixed sodium-potassium vapor. We present data on the excitation spectrum, forward to backward asymmetry, temporal dependence, and the laser power dependence of this emission. We speculate that twophoton photodissociation of the NaK molecule is responsible for this emission.     

Upconversion fluorescence property of Er/Yb-codoped novel bismuth-germanium glass

Infrared-to-visible upconversion fluorescence property of Er³⁺/Yb³⁺-codoped novel bismuth-germanium glass under 975 nm LD excitation has been studied. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. The structure of the bismuth-germanium glass has been investigated by peak-deconvolution of FT-Raman spectrum, and the structural information was obtained from the peak wavenumbers. This novel bismuth-germanium glass with low maximum phonon energy (∼750 cm⁻¹) can be used as potential host material for upconversion lasers.     

Time-resolved fluorescence spectra of a bichromophoric molecule, 2-methyl-1,2,3,4-tetrahydroisoquinoline in various media

Time-resolved fluorescence spectra of a title molecule (with benzene and aliphatic amine parts) in various media, after excitation by several lasers were observed to complement the previous work by conventional spectroscopy [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. Though complex with many new features, the results were roughly consistent with the previous ones. The significant conclusions are as follows: (1) The emission to be ascribed to the amine (N) part, with more than one component (of nN and aN types) is observed not only for the acetonitrile solution (as previously reported) but also for all the other media. (2) Contrary to the case of a nonpolar hexane solution, both of N fluorescences in the other media reveal unusually long-lived decay components. This can be interpreted by assuming the so-called charge-transfer-to-solvent (CTTS) state that is nonfluorescent and lies just below the fluorescent state. (3) This observation in the protic media can also be taken as another evidence of the peculiar hydrogen bonding between this amine and the protic solvent molecules [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. (4) Thus, the unexpectedly large quantum yields of N fluorescences in the polar media are now interpreted as arising due to the slow S₁^N→(CTTS)→S₀ internal conversions.     

Optical and photophysical investigation of Meso, Proto and Hematoporphyrin(IX)dimethylester doped hybrid borate glasses

Hybrid borate glasses containing different concentrations (0.5-2.0 mg in 12 g of boric acid) of Mesoporphyrin(IX)dimethylester, Protoporphyrin(IX)dimethylester and Hematoporphyrin(IX)dimethylester were prepared by rapid melt quench technique at 230 °C. The hybrid glass samples were characterized by X-ray diffraction, optical absorption, steady state and time-resolved fluorescence emission. The optical absorption spectrum shows red-shift in Soret band along with change in Q-band pattern. The intensity of Q-band was found to increase with increase in the concentration of porphyrin in the glass. Steady state emission spectrum shows strong S₂→S₀ emission in the range 462-495 nm and blue shift in S₁→S₀ emission. Time-resolved fluorescence emission and fluorescence excitation spectra showed that different structures of porphyrins were exist in the glass samples. The variation in the spectral behaviour in the glass was correlated with those in solution medium and possible structures of porphyrin in borate glass were explored.     

Luminescence from the Pr 4f5d and S0 states in LiLaP4O12

The photoluminescence and excitation spectra of Pr³⁺ activated LiLaP₄O₁₂ has been investigated in the 10-300 K temperature region. At all temperatures, the luminescence consists of optical transitions emanating from both the Pr³⁺ 4f¹5d¹ and the ¹S₀ states. However, at low temperatures the emission spectrum is dominated by the intraconfiguration emission transitions emanating from the Pr³⁺¹S₀ state. With increasing temperature, there is an exchange of intensity between the two emitting states; emission transitions from the ¹S₀ state exhibit strong intensity quenching while the 4f¹5d¹→4f² emission transitions reveal intensity gain. These results are explained on the basis of thermal population of the 4f¹5d¹ state by the ¹S₀ state. The energy barrier of 0.05 eV (403 cm⁻¹) for the nonradiative process is determined from the temperature dependence of the ¹S₀ lifetime.     

Steady-State Spectroscopic and Fluorescence Lifetime Measurements of New Two-Photon Absorbing Fluorene Derivatives

Steady-state excitation anisotropy, lifetimes, and time-resolved emission spectra of new 2-photon absorbing fluorene derivatives were measured in aprotic solvents at room temperature. Excitation anisotropy spectra in viscous silicon oil allowed the determination of the spectral position of three electronic transitions S₀ S₁, S₀ S₂, S₀ S₃ (S_i, i = 1, 2, 3 are the singlet electronic states) and the angles ( 30°) between absorption S₀ S₁ and emission S₁ S₀ dipole moments for the first electronic transition. Solvate relaxation processes in the first excited state of the investigated fluorene molecules affect the lifetimes of these states, ₁, so that experimental values of ₁ do not correspond to those calculated by Strickler and Berg theory. The influence of the molecular concentration on the fluorescence quantum yields and ₁ have been investigated.     

Luminescence spectroscopy of the Bi single and dimer centers in Y3Al5O12:Bi single crystalline films

Luminescence of the Bi³⁺ single and dimer centers in UV and visible ranges is studied in YAG:Bi (0.13 and 0.27 at% of Bi, respectively) single crystalline films (SCFs), grown by liquid phase epitaxy from a Bi₂O₃ flux. The cathodoluminescence spectra, photoluminescence decays, and time-resolved spectra are measured under the excitation by accelerated electrons and synchrotron radiation with energies of 3.7 and 12 eV, respectively. The energy level structure of the Bi³⁺ single and dimer centers was determined. The UV luminescence of YAG:Bi SCF in the bands that peaked at 4.045 and 3.995 eV at 300 K is caused by radiative transitions of Bi³⁺ single and dimer centers, respectively. The excitation spectra of UV luminescence of Bi³⁺ single and dimer centers consist of two dominant bands, peaked at 4.7/4.315 and 5.7/6.15 eV, related to the ¹S₀→³P₁ (A band) and ¹S₀→ ¹P₁ (C-band) transitions of Bi³⁺ ions, respectively. The excitation bands that peaked at 7.0 and 7.09 eV are ascribed to excitons bound with the Bi³⁺ single and dimer centers, respectively. The visible luminescence of YAG:Bi SCF presents superposition of several wide emission bands peaking within the 3.125-2.57 eV range and is ascribed to different types of excitons localized around the Bi³⁺ single and dimer centers. Apart from the above mentioned A and C bands the excitation spectra of visible luminescence contain wide bands at 5.25, 5.93, and 6.85 eV ascribed to the O²⁻→Bi³⁺ and Bi³⁺→Bi⁴⁺ + e charge transfer transition (CTT) in Bi³⁺ single and dimer centers. The observed significant differences in the decay kinetics of visible luminescence under excitation in A and C bands of Bi³⁺ ions, CTT bands, and in the exciton and interband transitions confirm the radiative decay of different types of excitons localized around Bi³⁺ ions in the single and dimer centers.     

Theoretical investigation of the ground and excited state of silylated coumarin

We present ground and excited state properties of silylated coumarin dyes. We have calculated the energies and dipole moments of ground and excited states of silylated coumarins and some coumarin derivatives. Using CIS we find a good agreement with experimental S₀→S₁ excitation energies. Silylation of dye molecules had minor effect on the transition energies. On the basis of theoretical results, we conclude that silylated dye will have improved long-term photostability compared to its unsilylated counterpart due to its covalent bonding with the host matrix.     

Optogalvanic detection of velocity-selective optical pumping in an open, cascade atomic medium

We performed two-color spectroscopy of the (4s²) ¹S₀ → (4s4p) ¹P₁ → (4p²) ¹D₂ calcium atomic transition and observed velocity-selective optical pumping in a calcium hollow cathode lamp by means of optogalvanic detection. The optical pumping signature in optogalvanic detection is compared to that of fluorescence and transmission detections. The optogalvanic technique is found to be a very sensitive method of detecting optical pumping and could be used in distinguishing optical pumping from electromagnetically induced transparency.     

Structural and upconversion fluorescence properties of Er/Yb-codoped oxychloride lead-germanium-bismuth glass

Structural and infrared-to-visible upconversion fluorescence properties of Er³⁺/Yb³⁺-codoped oxychloride lead-germanium-bismuth glass have been studied. The Raman spectrum investigation indicates that PbCl₂ plays an important role in the formation of glass network, and has an important influence on the upconversion luminescence owing to lower phonon energy. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively, were observed at room temperature. The quadratic dependence of the 525, 546, and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs under 975 nm excitation.     

LIF excitation spectra for S0 → S1 transition of deuterated anthranilic acid COOD, ND2 in supersonic-jet expansion

Laser induced fluorescence (LIF) excitation spectrum for the S₀ → S₁ transition of anthranilic acid molecules deuterated in the substituent groups (COOD, ND₂) was investigated. Analysis of the LIF spectrum allowed for the assignment of the six most prominent fundamental in-plane modes of frequencies up to ca. . The experimental results show good correlation with the frequency changes upon deuteration computed with CIS (CI-Singles) and TD-DFT for the S₁ state. Deuteration induced red-shifts of the identified fundamental bands are used for examination of the alternative assignments proposed in earlier studies. Potential energy distributions (PED) and overlaps of the in-plane normal modes with frequencies below indicate that the correspondence of the respective vibrations of the deuterated and non-deuterated molecule is very good. A blue-shift of the 00 transition due to the isotopic substitution, is equal to . This relatively large value is caused primarily by a significant decrease of the N-H stretching frequency associated with the increase of strength of the intramolecular hydrogen bond upon the electronic excitation. The deuteration shift of the 00 band was interpreted in terms of the differences of the zero point energy (ZPE) between the S₀ and S₁ electronic states, computed with DFT and TD-DFT methods, respectively.     

Spectral performance and intensive green upconversion luminescence in Er/Yb-codoped NaY(WO4)2 crystal

Using Czochralski (CZ) pulling method, an Er³⁺/Yb³⁺-codoped NaY(WO₄)₂ crystal was prepared. Absorption spectra, emission spectra and excitation spectra of this crystal were measured at room temperature. Some optical parameters, such as intensity parameters, spontaneous emission probabilities and lifetimes, were calculated from absorption spectra with Judd-Ofelt (J-O) theory. Upconversion luminescence excited by a 970 nm diode laser was studied. In this crystal, green upconversion luminescence is particularly intensive. Energy transfer mechanisms that play an important role in upconversion processes were analyzed. Two cross-relaxation processes: ⁴G_11/2 + ⁴I_9/2 → ²H_11/2 (or ⁴S_3/2) + ²H_11/2 (or ⁴S_3/2), and ⁴G_11/2 + ⁴I_15/2 → ²H_11/2 (or ⁴S_3/2) + ²I_13/2, which contribute to the intensive green luminescence under 378 nm excitation, were put forward. Background energy transfer ⁴G_11/2(Er³⁺) + ²F_7/2(Yb³⁺) → ⁴F_9/2(Er³⁺) + ²F_5/2(Yb³⁺) was also demonstrated.