Resonance multiplex cars of fluorescing acridines

Resonance enhanced coherent anti-Stokes Raman scattering (CARS) spectra have been obtained for the highly fluorescing acridine dyes, acridine orange and proflavine, in dilute methanol solutions at submillimolar concentrations. Spectra have also been taken in the multiplex mode by the use of a broad-band Stokes laser and a Vidicon OMA detection system. Several Raman bands are observed in the 1100–1600 cm^?1 region originating from the acridine ring modes. Upon decreasing the beam crossing angle a continuous transition from the normal CARS spectrum to a negative spectrum in the nonresonant background is observed.     

Stokes/anti-stokes intensity ratio in the resonance region

Relative intensities of the Stokes and anti-Stokes Raman lines associated with the I-I stretching mode of I₂ and symmetric stretching mode of MnO^?₄ are presented. The data indicate that the maxima in the excitation profile of the anti-Stokes scattering are shifted from those of the Stokes scattering. The experimental Stokes/anti-Stokes intensity ratios agree with the theoretical values obtained with parameters from the electronic absorption spectra.     

Origin of negative and dispersive features in anti-Stokes and resonance femtosecond stimulated Raman spectroscopy

Femtosecond stimulated Raman spectroscopy is extended to probe ground state anti-Stokes vibrational features. Off resonance, negative anti-Stokes features are seen that are the mirror image of the positive Stokes side spectra. On resonance, the observed dispersive lineshapes are dramatically dependent on the frequencies of the picosecond pump and femtosecond probe pulses used to generate the stimulated Raman spectra. These observations are explained by the contributions of the inverse Raman and hot luminescence four-wave mixing processes discussed by Sun et al. [J. Chem. Phys. 128, 144114 (2008)], which contribute to the overall femtosecond stimulated Raman signal.     

Spectroscopy of the E band of SO2 with a frequency-doubled single-mode dye laser

The rotational structure of the E band of SO₂ between 32720 and 32900 cm^?1 has been investigated by absorption spectroscopy with reduced Doppler width in a cooled cell at 190 K using a frequency-doubled cw single-mode dye laser. More than 400 lines in this band could be assigned, starting from a former partial analysis by Hamada and Merer. Severe perturbations in the upper state impede the assignment and prevent the unambiguous identification of many other lines in the spectrum. From the measured lines term values and molecular constants of the upper levels are derived. A comparison with spectra of very high resolution, taken in a collimated supersonic SO₂ beam demonstrates that the actual line density is by far higher than the spectral resolution in the cooled cell.     

Stimulated Raman scattering from H2+ ions

The observation of optical signals due to light scattering from H₂⁺ molecular ions is reported and discussed. By focusing Q-switched 1064 nm Nd : YAG laser light in H₂ at 20 bar, optical frequencies have been generated. They are assigned partly to stimulated Raman scattering from H₂⁺ and partly from H₂ molecules. The scattered radiation (Stokes-shifted 1064 nm beam) was transformed into visible light via higher-order four-wave mixing processes. The frequencies thus obtained could be observed with the naked eye if the scattered light was dispersed and projected on a white screen. The temperature of the gas in the focal region of the laser beam was estimated to be 1030 ± 300 K.     

Infrared and Raman spectra and normal coordinate calculations for methylisothiocyanate

The infrared spectra (3200-50 cm^?1) of gaseous and solid CH₃NCS and CD₃NCS and the Raman spectra (3200-10 cm^?1) of the liquids and solids have been recorded. The spectra have been interpreted on the basis of a “pseudo-symmetric top” with C_3v symmetry. An assignment of the fundamental vibrations in both molecules, based on their infrared band contours, depolarization values and group frequencies, is given and discussed. Particularly interesting is the low-frequency region where band maxima were observed at 152 and 80 cm^?1 for CH₃NCS and 139 and 71 cm^?1 for CD₃NCS in the infrared spectra of the gases. A normal coordinate analysis has also been carried out based on C_3v symmetry. Considerable mixing was found between the C_αN stretch and NCS symmetric stretch in both isotopic species. The other normal modes in CH₃NCS are reasonably pure but, for the CD₃NCS molecule, considerable mixing was found between the CD₃ stretches and NCS antisymmetric stretch. The proposed vibrational assignment and the results of the normal coordinate calculations are discussed and compared with the results obtained for similar molecules.     

New directions of matrix ir-spectroscopy

By use of thermal molecular beam IR matrix spectroscopy and IR irradiation in selected frequency ranges the vibrational spectra of conformers of 1,2-difluoroethane and methylvinylether will be discussed. The former molecule affords a case, where by comparison of CO₂ laser and 3000 cm^?1 irradiation the barriers to interconversion gauche?trans may be estimated. Methylvinylether on the other hand is a molecule, whose conformers may be interconverted by a 1-photon process in the 3000 cm^?1 region, but not by photons with frequency lower than 1400 cm^?1.     

Na-beam cooling by a mode-locked laser

Controlled mode-locked laser cooling of sodium atoms has been demonstrated for the first time. The broadband laser spectrum covers most of the Doppler-broadened atomic resonance spectrum. Atoms of a broad velocity range are thus decelerated simultaneously. In order to stop this process at a defined atomic velocity a two-mode laser beam tuned to resonance with both sodium groundstate levels is copropagating with the atomic beam and counterpropagating to the mode-locked laser beam. In this optical molasses sodium atoms ofv=20 m/s have been piled up to densities of about 2·10⁶ cm^?3. The density dependence on variable laser parameters has been investigated systematically.     

Time resolved molecular spectroscopy using high power solid state lasers in pulse transmission mode. A re-examination of the Sn← S1 spectra of naphthalene and anthracene

A nanosecond laser spectrometer consisting of a 3nsec ruby/Nd PTM laser, fast detection system and high brightness analysing source is described. An analysis of the geometry considerations is given for crossed beam and collinear arrangement. The excited-state absorption spectra of naphthalene in 3MP at 85°K and 293°K from 14000 to 30000 cm^?1 are given. The results provide a direct method to evaluate the quantum yields for fluorescence φ_f and intersystem crossing φ_T. Also the excited-state absorption spectra of anthracene in PMM from 16000 to 26000 cm^?1 and in 3MP from 26000 to 36000 cm^?1 are reported.     

Surface-enhanced raman scattering from poly(4-vinyl pyridine)

Surface-enhanced Raman scattering (SERS) has been observed for poly(4-vinyl pyridine) absorbed onto silver island films. Bands near 1219 and 1613 cm^?1, which are weak in normal Raman spectra of PVP, are strong in SERS spectra, and the band near 1020 cm^?1, which is the strongest band in the normal spectra, is relatively weak in SERS. The strongest bands in the SERS spectra all belong to the same symmetry species as α_ZZ, implying that the pyridine moieties are adsorbed through the nitrogen atoms with a vertical conformation. The ring breathing mode of the pyridine rings is observed near 1020 cm^?1, a frequency characteristic of pyridinium ions or coordinated pyridine, providing further evidence for adsorption through the nitrogen atoms. Silver catalyzed photooxidation, which can lead to the appearance of artifacts in SERS spectra, particularly of polymers, can be reduced by overcoating SERS samples with thin films of polymers such as poly(methyl methacrylate) that have low Raman scattering cross sections.     

New Spectral Techniques: Time-Resolved Fourier-Transform Spectroscopy and Two-Color Laser-Induced Grating Spectroscopy

Time-resolved Fourier-transform spectroscopy and two-color laser-induced grating spectroscopy are two new techniques recently employed in this laboratory. We recorded emission in the near infrared region during laser photolysis of HONO₂ with a step-scan Fourier-transform spectrometer and achieved temporal resolution in the microsecond range and spectral resolution of 0.1 cm¹. Rotationally resolved emission lines of the (0,0) band of the D ²∑⁺ →A ²∑ ⁺ transition of NO in the region 8900-9300 cnv^?1 with irregular relative intensities were observed when an ArF excimer laser was used to photodissociate HONO₂. The spectroscopic parameters of both D ²∑⁺ and A ²∑⁺ states agree with those previously reported. When a narrow-band ArF laser was used, selective rotational levels of the D state of NO were populated depending on the wavelength of the ArF laser. Our results indicate that absorption of a 193-nm photon by NO(υ″ = 1) is responsible for the observed emission. To test the technique of two-color laser-induced grating spectroscopy, we employed the B ³II_0U⁺-X ¹∑_g ⁺ system of I₂. Background-free spectra with transitions involving rotationally selected states were recorded. Various experimental schemes were employed with population gratings formed in either the B or X state. Signals due to different four-wave mixing schemes were distinguished by variation of relative timing between the grating beams and the probe beam.     

Monomere und dimere Chrom(III)-Phthalocyanine: Synthese und Eigenschaften von Hydroxopyridinophthalocyaninatochrom(III) und μ-Oxodi(pyridinophthalocyaninatochrom(III))

Monomeric and Dimeric Chromium(III) Phthalocyanines: Synthesis and Properties of Hydroxopyridinophthalocyaninatochromium(III) and μ-Oxodi(pyridinophthalocyaninatochromium(III)) Heating of ?[Cr(OH)Pc^2?]”? in pyridine (Py) gives the paramagnetic (T = 273 K) complexes [Cr(OH)(Py)Pc^2?] (μ_Cr = 3.84 μ_B) and [(Cr(Py)Pc^2?)₂O] (μ_Cr = 1.24 μ_B) by consecutive substitution and condensation reactions. The UV-VIS spectra are characterized by the typical B, Q, and N regions of the Pc^2? ligand being shifted hypsochromically for the dimer with respect to the monomer due to excitonic coupling (1.5 kK). Regions of weak absorbance between 8 and 13 resp. 19 kK are assigned to trip-quartet transitions for both complexes. A weak band at 870 cm^?1 in the FIR/MIR spectra is assigned to v_as(Cr? O? Cr). In the resonance Raman(RR) spectra v(Cr? O) at 514 cm^?1 resp. v_s(Cr? O? Cr) at 426 cm^?1 is selectively enhanced. Further strong RR-lines of the μ-Oxo dimer at 110 and 631 cm^?1 are assigned to a (Py? Cr? O)- resp. internal pyridine deformation of a_1g symmetry. An assignment as 2v_as(Cr? O? Cr) is proposed for the remarkable RR line at 1740 cm^?1.     

Accurate measurement of the pressure broadening of the ν1 Raman line of CH4 in the 1–50 atm region by inverse Raman spectroscopy

The lineshape of the ν₁ Raman band of methane is measured as a function of pressure between 1 and 50 atm by inverse Raman spectroscopy using the 488 nm output of a cw Ar⁺ laser as a probe beam and the output of a pulsed dye laser as a Stokes pump beam. The linewidth is found to increase linearly in this pressure region, and the fwhm Δν (in cm^?1) can be expressed as Δν = 0.32 + 0.012p, p being the methane pressure in atm.     

A study of the electronic spectra of 9-fluorenone

The absorption and MCD spectra of 9-fluorenone are measured. The CD spectra of the β-cyclodextrin complex with 9-fluorenone are also measured. The assignment for the first (≈26.0 × 10³ cm^?1) and fourth (≈48.0 × ³ cm^?1) absorption band has been determined from the sign of the CD spectra by reference to the observed MCD spectra.     

Resonance Raman scattering from triplet states of acridine and anthracene

By preparing a population of triplet states through excitation with a laser pulse of 308 nm, we could determine the resonance Raman spectra of acridine and of anthracene in their lowest (π π*) state, T₀. Thirty Raman lines in the region between 200 and 2000 cm^?1 are reported for acridine in the T₀ state. These are attributed to either a₁ or b₂ vibrational modes. Nineteen Raman lines between 500 and 2000 cm^?1 are reported for anthracene in the T₀ state.     

Infrared molecular beam depletion spectroscopy of size-selected methanol clusters

Molecular beam depletion spectroscopy has been employed to study the dissociation of small methanol clusters in the spectral region between 1000 and 1100 cm^?1 which covers thev ₈ CO stretch (1033.5 cm^?1) and thev ₇ CH₃ rock (1074.5 cm^?1) monomer vibrations. Size selection has been achieved by dispersing the (CH₃OH) _n cluster beam by a secondary He beam. Aside from the recently published CH₃OH dimer absorption bands at 1026.5 and 1051.6 cm^?1 which are assigned to the excitation of the CO stretching vibrations in the non-equivalent subunits of the hydrogen-bonded complex, a previously unobserved band was found at 1071.3 cm^?1. This absorption band is attributed to the excitation of the CH₃ rocking vibration in the dimer. It appears that this transition which is very weak in the free methanol monomer receives substantial oscillator strength due to the intermolecular interaction in the complex. A splitting of this band could not be observed. The trimer and tetramer spectra feature single peaks for the CO stretching vibration being centered at 1042.2 cm^?1 and 1044.0 cm^?1, respectively. This observation is consistent with the cyclic structures of these species. The trimer and tetramer rocking vibrations are observed near 1060.5 cm^?1 but cannot be localized exactly, due to a gap in the CO₂ laser tuning range.     

Shaping femtosecond coherent anti-Stokes Raman spectra using optimal control theory

Optimal control theory is used to tailor laser pulses which enhance a femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) spectrum in a certain frequency range. For this aim the optimal control theory has to be applied to a target state distributed in time. Explicit control mechanisms are given for shaping either the Stokes or the probe pulse in the four-wave mixing process. A simple molecule for which highly accurate potential energy surfaces are available, namely molecular iodine, is used to test the procedure. This approach of controlling vibrational motion and delivering higher intensities to certain frequency ranges might also be important for the improvement of CARS microscopy.     

Picosecond time-resolved cars in isotopically mixed crystals of benzene

Time-resolved coherent anti-Stokes Raman experiments are reported for the benzene crystal 991 cm^?1 mode and in mixed C₆H₆/C ₆D₆ crystals. Addition of C₆D₆ results in an increase in the rate at which the excitation is trapped. This is explained by the recent theory of Velsko and Hochstrasser which predicts that the trapping rate should undergo a maximum at some isotopic impurity concentration, consistent with observations from time and frequency domain studies. A proper convolution procedure for CARS experiments in the time domain is presented.     

The Structural and Optical Properties of 1,2,4-Triazolo[4,3-a]pyridine-3-amine

The structural and spectroscopic properties of a new triazolopyridine derivative (1,2,4-triazolo[4,3-a]pyridin-3-amine) are described in this paper. Its FTIR spectrum was recorded in the 100–4000 cm⁻¹ range and its FT-Raman spectrum in the range 80–4000 cm⁻¹. The molecular structure and vibrational spectra were analyzed using the B3LYP/6-311G(2d,2p) approach and the GAUSSIAN 16W program. The assignment of the observed bands to the respective normal modes was proposed on the basis of PED calculations. XRD studies revealed that the studied compound crystallizes in the centrosymmetric monoclinic space group P2₁/n with eight molecules per unit cell. However, the asymmetric unit contains two 1,2,4-triazolo[4,3-a]pyridin-3-amine molecules linked via N–H⋯N hydrogen bonds with a R₂²(8) graph. The stability of the studied molecule was considered using NBO analysis. Electron absorption and the luminescence spectra were measured and discussed in terms of the calculated singlet, triplet, HOMO and LUMO electron energies. The Stokes shifts derived from the optical spectra were equal to 9410 cm⁻¹ for the triazole ring and 7625 cm⁻¹ for the pyridine ring.