Anomalous fluorescence properties of 4-N,N-dimethylaminobenzoic acid in polar solvents

4-N,N-Dimethylaminobenzoic acid exhibits anomalous fluorescence in polar and hydrogen-bonding solvents. The fluorescence spectra and kinetics suggest that this arises due to the formation of a ground-state dimer or higher polymer. Preliminary measurements in hexane containing small amounts of polar acetonitrile do not rule out the possibility of exciplex formation also occurring.     

Influence of surfactants on the fluorescence and absorption spectra of erythrosin in aqueous solution

The effect of certain non-ionic, anionic and cationic surfactants on the fluorescence and absorption spectra of erythrosin has been studied. Shifts towards longer wavelengths in absorption and fluorescence peaks have been observed. Also, there appears to be a marked enhancement in the fluorescence intensity of erythrosin on adding small amounts of surfactants. The shift in the absorption peak wavelength appears to be due to the binding of the surfactant with dye molecules. The enhancement in the fluorescence intensity is attributed to the disaggregation of erythrosin dye dimer and multimer forms into the monomeric form. The change in the geometry of dye molecules in the presence of cationic surfactants has also been discussed. Enhancement in the fluorescence intensity on the addition of ethanol has been observed.     

Fluorescence ofp-N,N-dimethylaminobenzonitrile incorporated in pores of molecular sieves

The donor-acceptor-substituted aromatic moleculep-N, N-dimethylaminobenzonitrile (DMABN) is known to show a characteristic dual twisted intramolecular charge transfer (TICT) fluorescence with a pronounced solvent dependence. Despite the two-band structure of the fluorescence from DMABN incorporated within pores of the molecular sieves AlPO-5, SAPO-5, ZSM-5, and silicalite, there is no indication for TICT-state emission.     

Shapes and shifts in the oxygen Auger spectra

The oxidation of silicon and platinum single crystal faces, of polycrystalline supported catalysts and of some alloy surfaces has been studied by AES and as far as possible by LEED. A comparison of the oxygen Auger spectra obtained during the oxidation process with those found on oxides has been made; it shows that the modification of the fine structure of the oxygen Auger peaks gives some information about the binding state of oxygen. Two different structures, which compete one with the other, are described. In one case, a spectrum where three lines dominate is obtained; in the other case, a “quasi-atomic” spectrum characterized by five features is observed: multiplet splitting in the two-hole final state is predominant. Besides these differences in the fine structure of the Auger spectra one can notice shifts of several eV for the main feature. They have been correlated with the various observed LEED patterns. Physisorption, chemisorption, solution of oxygen in the metal lattice, growth of ordered or amorphous oxides are the different possibilities which are discussed.     

Isotope shifts in spectra of molecular liquids

In the IR absorption spectra of low-temperature molecular liquids, we have observed anomalously large isotope shifts of frequencies of vibrational bands that are strong in the dipole absorption. The same effect has also been observed in their Raman spectra. At the same time, in the spectra of cryosolutions, the isotope shifts of the same bands coincide with a high accuracy (±(0.1–0.5) cm^–1) with the shifts that are observed in the spectra of the gas phase. The difference between the spectra of examined low-temperature systems is caused by the occurrence of resonant dipole–dipole interactions between spectrally active identical molecules. The calculation of the band contour in the spectrum of liquid freon that we have performed in this work taking into account the resonant interaction between states of simultaneous transitions in isotopically substituted molecules can explain this effect.     

Calculation and interpretation of the absorption and fluorescence spectra of indole in the isolated state and aqueous solution

We have calculated the vibronic absorption and fluorescence spectra of the first (¹ L _b ) and second (¹ L _a ) electronic transitions of indole in the isolated state and aqueous solution. The vibrational structure of the absorption and fluorescence spectra has been interpreted. The influence of the aqueous solution on the vibronic spectra has been shown.     

Laser spectroscopic measurement of isotope shifts of transitions 3d-4p in the ionic spectra of argon,chlorine and sulphur

By means of collinear laser spectroscopy at ion beams of Ar⁺, S⁺ and Cl⁺ the isotope shifts of a total of twelve lines could be measured. All the lines are of the type 3p ^n?1 3d→3p ^n?14p (3p ⁿ being the proper ground configuration of the ions). All the measured shifts are unusually large and prevailingly due to a strong specific mass effect or momentum correlation of the 3d electron with the innerp-shells. The measured shifts could be quantitatively reproduced by computation of the inherent Vinti integrals.     

Absorption,fluorescence, and fluorescence excitation spectra of free molecules of indole and its derivatives

We have obtained and analyzed the absorption, fluorescence, and fluorescence excitation spectra of indole vapor, N-acetyl-L-tryptophan vapor, and 3-indole aldehyde vapor. From analysis of the dependence of the fluorescence spectrum of the free indole molecules on the wavelength of the exciting radiation λ_ex, it follows that emission of fluorescence occurs when the molecules undergo a transition from the one electronically excited state ¹L_b. The fluorescence spectra of the studied compounds are insignificantly different, suggesting a major role for the indole chromophore in formation of the compounds. The absorption spectrum of N-acetyl-L-tryptophan, in which the group of atoms is added to the indole ring through a-C-C bond, is similar to the spectrum of indole, while the spectrum of 3-indole aldehyde is significantly different from the indole spectrum due to the effect of the C=O group conjugated with the indole ring. The fluorescence excitation spectra are considerably different from the absorption spectra. This is associated with the strong dependence of the quantum yield for the free molecules on λ_ex. Qualitatively, they are mirror-symmetric to the fluorescence spectra of the stodied compounds. Analysis of the data obtained provides a basis for assuming that in the case of free molecules of indole and its derivatives, the ¹L_a absorption in the extreme long-wavelength region of the spectrum does not overlap ¹L_b absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 218–222, March–April, 2007.     

Surface core level shifts in photo-electron spectra from the Ca, Sr and Ba titanates

Photoelectron binding energy (BE), shifts observed in core level spectra of Ca, Sr and Ba present at the outer most surface with respect to the bulk in the respective single crystal titanates can be correlated to the inverse of their respective electro-negativities. Such trends can be explained within the context of the charge potential model. This model, which does not account for final state effects, indicates that (a) the direction of the BE shift results from chemical environment variations (an inter-atomic effect sometimes referred to in Madulung constant terms), and (b) BE shift variations result from electron density variations on the atom the photo-electron emanated from (an intra-atomic effect, which can also be relayed in ionic radii and electro-negativity terms).     

Calculations of pressure induced widths and shifts in microwave spectra

Calculations of the width and shift of pressure induced spectral lines in gases at low pressures in the microwave region of the electromagnetic spectrum are presented. These calculations are based on an extension of the Anderson-Tsao-Curnutte theory and are compared with those based on the quantum mechanical model developed by Di Giacomo and Cattani.     

Simulation study of solvent shifts of vibrational overtone spectra

Buckingham's theory of the solvent shift of vibrational spectral frequencies predicts that the shift of the v = 0 → n overtone transition is n times the shift of the fundamental v = 0 → 1. We test this prediction by molecular dynamics simulations using existing intermolecular potential models for liquid N₂ and dilute N₂ in liquid Ar, at standard state conditions. We extend Buckingham's theory by including additional intramolecular potential and perturbation terms which lead to solvent-induced anharmonicity, i.e. O(n ²) terms in the solvent shift. The simulations show that Buckingham's prediction is not accurate for N₂ at standard liquid state conditions. We find that at these conditions there is a significant positive O(n ²) contribution to the solvent shifts and that for n ～ 20 the shifts change sign from red to blue. Simulation results and indirect evidence from shock wave experiments with liquid N₂ show that Buckingham's prediction is more accurate for high-pressure high-temperature conditions, where the shifts are blue and only slightly nonlinear in n.