Variation in the fluorescent background in Raman spectra of distilled water purified by different methods

The contribution of impurity fluorescence was determined in the water Raman spectra excited by the second harmonic (λ = 532 nm) of a pulsed Nd:YAG laser. Water samples prepared by different techniques (tap water (undistilled), distilled water, Milli-Q water, water for injections, and water subjected to cavitation treatment) were investigated. The Raman (bands at ν ₂ ∼ 1550 cm⁻¹ and ν ₃ ∼ 3400 cm⁻¹) and fluorescence (Stokes shift 2500 cm⁻¹) signals were separated spectrally and according to the differences in the emission kinetics. It was established that all investigated samples, including distilled and specially purified water for injections, exhibit afterglow. The highest sensitivity to the presence of impurities was revealed near ∼ 2500 cm⁻¹. The least contribution to the fluorescence signal was found in the water for injections.     

Fluorescence of jet-cooled naphthalene: Emission spectra, lifetimes and quantum yields

Fluorescence spectra of naphthalene, C₁₀H₈, were obtained in the laboratory under conditions which provide an appropriate simulation of the cometary conditions: super-cooled gas phase molecules in a collision-free environment. Five spectra were recorded, the excitation energies ranging from 1422 to 5293 cm⁻¹ above the first electronic state S₁ at 32 020 cm⁻¹. A comparison with previous jet-cooled naphthalene fluorescence spectra obtained by Beck et al. [1] and Hermine [2] shows that the former results are not consistent with the present ones. Spectra obtained by Beck et al. show weaker intensities at greater wavelengths compared to those obtained by Hermine and ourselves. We also measured the fluorescence lifetimes by recording the fluorescence decay as a function of time after the excitation of the molecules by monochromatic lasers and deduced the fluorescence quantum yields. A synthetic emission spectrum under solar irradiation is obtained for astrophysical implications.     

Photophysical parameters for potential vapour-phase dye-laser media

The fundamental photophysical parameters of the organic scintillators, anthracene, 9, 10 dimethyl antracene (DMA), 9, 10 diphenyl anthracene (DPA), 2-(1-napthyl)-5-phenyloxazole (α-NPO) and 2, 2′-p-phenyl bis (5-phenyloxazole) (POPOP), were investigated in the liquid and vapour phases. Their ground state, triplet-triplet and fluorescence spectra were determined and accurate extinction coefficients obtained. Photodecomposition of POPOP vapour under 337 nm excitation was investigated in detail and a photodecomposition quantum yield of 1.1×10⁻² obtained at 568 K. The POPOP triplet state in the vapour phase is quenched by the addition of 1, 3, 5, 7 cyclo-octatetraene and a quenching rate constant of 2.9×10¹⁰ M⁻¹ s⁻¹ was determined.     

Fermi-type resonance in quasi-linear fluorescence excitation spectra of triazatetrabenzoporphine

The effect of deuteration of the central NH groups on the quasi-linear fluorescence and fluorescence excitation (with selective monitoring) spectra for triazatetrabenzoporphine, a close analog of phthalocyanine, has been investigated at 77K in n-nonane. Vibrational analysis of the spectra was carried out. The normal mode frequencies were determined for the electronic states S₀ (from fluorescence spectra) and S₁ (for fluorescence excitation spectra). It has been established that N-deuteration lowers the frequency of a vibration involving inplane NH bending down to ∼990 cm⁻¹ and leads to resonant vibrational-electronic (vibronic) interaction of Fermi-type resonance between the zero level of the S₂ state and the vibronic level of the S₁ state upon excitation of this mode. Thereby the possibility of the “vibronic analog of Fermi resonance” (a term coined by G. Herzberg) occurring in a simple (two-component) variant of phthalocyanine-type molecules has been shown. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 796–803, November–December, 2008.     

High resolution,rotation, vibration spectra of D2O in the region ofν 1 andν 3 bands

The infrared spectrum of D₂O from 2400 to 3000 cm⁻¹ has been analysed at a resolution better than 0·02 cm⁻¹. It was recorded at the Fourier transform spectrometer of the Kitt Peak National Observatory, Tucson. Ground state constants of the reduced Watson-Hamiltonian, ground state energies and transition for theν ₁ andν ₃ bands are reported. The effect of strong Coriolis resonances on the spectra is discussed. Work done at the Jet Propulsion Laboratory, Division of Stratospheric and Planetary Research California Institute of Technology, Pasadena, Ca (U.S.A.)     

Identification of the SO2 cold vibronic bands in the 32 200–33 300 cm−1 region

Summary The fluorescence excitation spectrum of SO₂ in the 32 200–33 300 cm⁻¹ energy region was recorded, at very low rotational temperature, in a pulsed supersonic jet. The band centres and relative intensities of about 60 well-resolved vibronic bands were determined in this region, which extends the previously available data by 800 cm⁻¹. Single vibronic level fluorescence spectra of two neighbouring vibronic bands in theD-band region along with a few filtered excitation spectra are also presented as an example of the resolution for the listed bands. The authors of this paper have agreed to not receive the proofs for correction.     

High-resolution coherent stokes Raman spectroscopy of theν 1 andν 3 bands of methane

Coherent Stokes Raman spectra of the ν₁ and ν₃ bands of CH₄ have been recorded in mixing two pulsed lasers (ruby and dye) of very good spectral and spatial quality. The results show a resolution of about 0.010 cm⁻¹ for a 10 Torr pressure, corresponding in great part to Doppler broadening.     

Polarized Fluorescence of Complex Molecules Being Excited by Low-Energy Electrons

Polarization of the fluorescence of the vapors of anthracene, perylene, 1,4-di(2,5-phenyloxazolyl)benzene (POPOP), and 2-phenyl-5-(4-biphenylyl)oxazole (BPO) upon excitation by a beam of monokinetic electrons with energy varying in the 5–300-eV range has been found. The electrical vector of radiation has a higher value in the direction perpendicular to the direction of the electron beam. For the substances studied, maxima of fluorescence polarization are observed that approximately coincide in position with the maxima of the excitation function. The maximum value of the fluorescence polarization degree of POPOP does not exceed 3.8%.     

Observation of simultaneous ν1(SF6) + ν3(NF3) and ν2(SF6) + ν3(NF3) transitions enhanced by the resonance dipole-dipole interaction with the ν1 + ν3 and ν2 + ν3 states of the SF6 molecule

IR spectra of the solution of SF₆ molecules in liquid NF₃ at 84 K have been recorded. In a solvent transmission window of 1500–1750 cm⁻¹, two wide absorption bands with pronounced peaks in the high-frequency part are observed. The profile of these bands is explained by the influence of the resonance dipole-dipole (RDD) interaction of the states of the simultaneous transition ν₁(SF₆) + ν₃(NF₃) and ν₂(SF₆) + ν₃(NF₃) with the states (ν₁ + ν₃) and (ν₂ + ν₃) of the SF₆ molecules, respectively. The use of three isotopic modifications ³²SF₆, ³³SF₆, and ³⁴SF₆ has allowed us to vary the resonance detuning and thus to change the strength of the RDD interaction. With the liquid near the melting point being represented as a close-packed cubic crystal, the profile was calculated and its spectral characteristics were determined. The frequencies of the main peaks coincide with the experimental values accurate to the error.     

Infrared spectra of S-and R-isomers of biologically active brassinosteroids

Comparative analysis of IR spectra of S-and R-isomers differing in the configuration of OH groups in the side chain of biologically active 24-epi-and 28-homocastasterones and 24-epi-and 28-homobrassinolides is carried out. Stretching vibration frequencies of H-bonded OH groups of isomers of corresponding brassinosteroids practically coincide. The optical density in maxima of these bands is higher in spectra of the R-isomers. Alteration in the configuration of the OH groups weakly influences also the band intensities of CH3, CH₂, and CH groups. Band intensities of stretching vibrations of associated C=O groups of S-and R-isomers also neglibibly differ from each other. Their frequency characteristics do not experience substantial changes. These features differ considerably in IR spectra of castasterones and brassinolides. For castasterones, the difference in frequencies of band maxima of free and bound C=O groups amounts to ∼15 cm⁻¹; for brassinolides, 23 cm⁻¹. Intensities of both bands are approximately equal in spectra of castasterones. The band intensity of free C=O groups of brassinolides is considerably lower than that of H-bonded ones. The above spectral differences can be used to identify these brassinosteroids. Frequencies of both symmetric and antisymmetric deformation vibrations of CH₃ and CH₂ groups are close in spectra of all brassinosteroids studied. The frequency of CH₂ in a CH₂-OC group belongs only to brassinolides; of deformation vibrations of CH in a CH-C=O group, to castasterones. The frequency of stretching vibrations of C-O-C and C-O groups is observed only in spectra of brassinolides. In the region 1130–900 cm⁻¹ of IR spectra of brassinosteroids, stretching vibrations of CC, CCH, and C-OH groups are predominantly observed. In the frequency range 1130–995 cm⁻¹, the optical density of band maxima of S-isomers is higher than that of R-isomers, which can be used to identify isomers. At the same time frequencies of corresponding bands of isomers practically coincide. Differences in the structure of the side chain of brassinosteroids do not influence essentially the frequency characteristics of the IR spectra. The exception is the band related to stretching vibrations ν(C23-OH) of the side chain which features a considerable frequency ν_max ≈ 983 cm⁻¹ only in spectra of R-isomers of homocastasterone and brassinolide. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 623–630, September–October, 2008.     

Experimental determination and interpretation of fluorescence and fluorescence excitation spectra of 1,2-benzanthracene cooled in supersonic jet

We measured the fluorescence and fluorescence excitation spectra of supersonic jet-cooled 1,2-benzanthracene. Using the MO/M8ST method, we calculated the frequencies of in-plane vibrations in the ground and first excited singlet electronic states, and, in the Franck-Condon approximation, we calculated the intensities of transitions between them. Experimental spectra are interpreted based on these data. In the fluorescence excitation spectrum, the position of the line of the 0–0 transition (26535 ± 1 cm⁻¹), which is the most intense, is determined.     

Generation of coherent thermal phonons in amorphous dielectrics at room temperature induced by four-photon interaction

Resonant responses of Mandelshtam-Brillouin scattering from longitudinal and transverse acoustic waves at frequencies of ν _LS = ±1.15 cm⁻¹ and ν _TS = ±0.7 cm⁻¹, respectively, and at frequency of ν _SS = ν _TS $ \sqrt 3 $ \sqrt 3 = ±0.43 cm⁻¹ were detected in K8 optical glass at room temperature using four-photon spectroscopy. We attribute this effect to the induced generation of a second sound wave (coherent thermal phonons). The mechanisms of generation and the possibility of practical application of the observed effect for express diagnostics of the quality of transparent materials are discussed.     

Investigation of excited-state proton transfer in 3-hydroxyflavone molecules

The dual fluorescence spectra of 3-hydroxyflavone molecules excited by electromagnetic radiation in the region of the S ₁ and S ₂ absorption bands in the temperature region of 20–80°C are studied using the dynamic quenching of the excited state. An analysis of the fluorescence parameters shows that heating the solution from room temperature to 60°C increases the proton transfer rate by a factor of 1.24 in the case of standard excitation into the main absorption band and even stronger (by a factor of 6.9) in the case of excitation into the second absorption band. The presence of a quencher reduces the yield of the two emission bands and noticeably increases the proton transfer rate, by a factor of 1.16 at room temperature and by a factor of 1.25 at 80°C. Upon excitation into the second singlet band, the transfer rate increases even more (especially at higher temperatures), by a factors of 1.24 and 3.5 for the same temperatures. The temperature dependences of the transfer rate constant allowed us to estimate the activation energies of the proton transfer reaction under different physical conditions and reach conclusions about the mechanism by which this reaction proceeds. It is found that the proton transfer activation energy decreases from 500 to 360 cm⁻¹ when measured in temperature ranges of 20–40 and 20–60°C. The introduction of a quencher with a concentration of 5 × 10⁻³ M increases the activation barrier to 534 and 471 cm⁻¹ in the same temperature ranges.     

The infrared and laser Raman spectra of K2Zn(SO4)2 · 6H2O

The Raman spectra of the single crystal of K₂Zn(SO₄)₂·6H₂O belonging toC _2h ⁵ space group in the 40–1200 cm⁻¹ region in different scattering geometries and their spectra ofthe microcrystalline salt in the 1500-50 cm⁻¹ region have been reported. The dynamics of the crystal has been described in terms of 186 phonon modes under the unit cell approximation. The weak bands in the region 400–900 cm⁻¹ have been assigned to the libratory modes of H₂O molecules in contradiction to the assignments reported by Ananthanarayanan. The ambiguities existing in the literature about the assignments ofν ₂ ^c andν ₅ ^c modes of [Zn(H₂O)₆]²⁺ have also been removed. The translatory and libratory modes of different units of the crystal have been identified and assignments are made using farir and Raman data on various isomorphous tutton salts. It has been inferred that both SO ₄ ²⁻ tetrahedron and [Zn(H₂O)₆]²⁺ octahedron undergo linear as well as angular distortions from their free state symmetries in the crystal.     

Quasiline fluorescence and absorption spectra of NH-isomers of octamethylisobacteriochlorin

Quasiline fluoresence and fluorescence excitation spectra of NH-isomers of 2,2,7,7,12,13,17,18-octamethylisobacteriochlorin (cis- and trans-) in polycrystalline matrices in n-hexane and n-octane at 4.2 K are obtained. A vibration analysis of the spectra in combination with the data of quasiline spectra of cyano-substituted octaethylisobacteriochlorin and octamethylporphin permitted a qualitative interpretation of the vibronic spectra of NH-isomers. It is inferred that for a trans-isomer, the 0–0 transition S₂⇃S₀ is localized in the region of electron-vibrational S₁⇃S₀ transitions; the interval S₂-S₁ has a magnitude of about 1300 cm⁻¹. Reported at the VIIIth International Conference on the Spectroscopy and Chemsitry of Poprhyrins and Their Analogs, Belarus, Minsk, September 22–26, 1998. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 79–85, January–February, 2000.     

FTIR spectra of plasticized high molecular weight PVC–LiCF3SO3 electrolytes

Fourier transform infrared spectroscopy studies have been conducted to investigate the interaction among components in a system of high molecular weight polyvinylchloride (PVC)–lithium trifluoromethanesulfonate (LiCF₃SO₃) incorporated with different type of plasticizers, namely, ethylene carbonate (EC), propylene carbonate (PC), and dibutylphthalate (DBP). Interaction between PVC and LiCF₃SO₃ was confirmed by C–H rocking mode at 1,255 cm⁻¹ for PVC shift to 1,252 cm⁻¹ in PVC–LiCF₃SO₃. The plasticizers’ carbonyl (C=O) oxygen atom which carries lone pair electrons interact with Li⁺ of LiCF₃SO₃ and methine hydrogen of PVC in LiCF₃SO₃–plasticizer system and PVC–plasticizer system, respectively. Changes in peaks assigned to 1,264 cm⁻¹ (ν _as(SO₃)), 1,033 cm⁻¹ (ν _s(SO₃)), 1,181 cm⁻¹ (ν _as(CF₃)), 1,230 cm⁻¹ (ν _s(CF₃)), 765 cm⁻¹ (δ _s(CF₃)), 644 cm⁻¹ (δ _s(SO₃)), 578 cm⁻¹ (δ _as(CF₃)), and 519 cm⁻¹ (δ _as(SO₃)) indicate the occurrence of complexation in the PVC–LiCF₃SO₃ system, LiCF₃SO₃–plasticizer system, and PVC–LiCF₃SO₃–plasticizer system.     

Interaction of Electrons with Indole,Tryptophan, and their Derivatives in the Gas Phase

The electron energy loss spectra (EELS) of indole, 3-indolyl propionic acid, 3-indolealdehyde, 3-dimethylaminomethylindole, tryptophan, and N-acetyl-L-tryptophan in the gas phase upon excitation by monokinetic electrons with an energy of E₀ = 11–50 eV are obtained. The structure of EELS is determined in the main by the indole chromophore; the side groups, except for the C=O group of 3-indolealdehyde, exert an insignificant influence. The energy of the lower triplet level ³L_a is 3.3 eV for indole and its derivatives and 3.2 eV for tryptophan and N-acetyl-L-tryptophan. Four singlet transitions in the region of 4.4–7.2 eV have been identified. The molecules studied, except for tryptophan, fluoresce in the gas phase on excitation by electrons. At low values of E₀ (10–25 eV), the fluorescence spectra are similar and are due to the indole fluorophore. Just as in the case of optical excitation, fluorescence on excitation by electrons is associated with the ¹L_b-S₀ transitions. An increase in the energy E₀ up to 60–80 eV leads to dissociation of a portion of the indole molecules and to the appearance of additional bands in the fluorescence spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 468–472, July–August, 2005.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Molecular Stark effect spectroscopy of diflavonol and inhomogeneous broadening of its electronic spectra in erythrocyte membranes

Using spectroscopy of the molecular Stark effect and fluorescence spectroscopy, we study the characteristics of diflavonol 3,7-dihydroxy-2,8-di(4-dimethylaminophenyl)-4H,6H-pyrano[3,2-g]chromene-4,6-dione (DFME), which demonstrates intramolecular charge and proton phototransfer. In the ground state, this dye has only one form and, in the excited state, it has two forms, i.e., normal and phototautomeric. We found that, for the normal form of DFME, the transition dipole moment that is responsible for the absorption (m _a ), the dipole moment in the equilibrium ground state (μ _g ), and the change of the dipole moment upon transition of the molecule in the excited Franck-Condon state (Δ ^a μ) are parallel. In the ground equilibrium state, the dipole moments in 1,4-dioxane and cyclohexane are equal to μg = 12.2 × 10⁻³⁰ C m and μ _g = 11.0 × 10⁻³⁰ C m, respectively. Upon excitation, they increase by Δ ^a μ = 61 × 10⁻³⁰ C m and Δ ^a μ = 50.2 × 10⁻³⁰ C m in these solvents. We study the spectral characteristics of DFME in organic solvents and erythrocyte membranes. A spectral inhomogeneity of DFME in erythrocyte ghosts is found. The inhomogeneous broadening of fluorescence spectra is manifested as a long-wavelength shift of the band of the normal form of DFME by 1640 cm⁻¹ upon excitation at the red edge of the absorption spectrum.     

Energy transfer in chemical dimers of porphyrins and chlorins by the methods of selective laser spectroscopy at 1.8–10 K

The methods of selective laser spectroscopy applied at 1.8–10 K to a glass-forming tetrahydrofuran-toluene (3∶1) mixture have revealed that in the dimers of tetrapyrrole compounds (ethane-bis-octaethylporphyrins, ethane-bis-Zn-octaethylchlorins, heterodimers of Zn-cyclopentane porphyrins) the exciton interactions (V₁₂≈118 cm⁻¹) and S-S-transfer of energy (of probability F≈11 sec⁻¹) are implemented under conditions of substantial inhomogeneous broadening (δF_1/2≈50 cm⁻¹). Upon excitation of a donor component in the dimers, one observes a strong quenching of its emission, the disappearance of the fine structure in the fluorescence spectra, a decrease in the efficiency of spectral hole burning by, approximately, an order of magnitude, and a 12-fold increase in their halfwidth. To whom correspondence should be addressed. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 500–504, July–August, 1999.