Influence of inhomogeneous broadening on resonance raman characteristic of metalloporphyrins and metallophthalocyanines

A recently proposed model that describes Q-state region depolarization dispersion curves of resonance Raman fundamentals of porphyrins (phthalocyanines) subject to asymmetric perturbations is extended to include the effects of inhomogeneous broadening of the intermediate states. The resulting depolarization dispersion curves and excitation profiles for perturbations of different symmetry are calculated and discussed. It is shown that experimental data for Pt-phthalocyanine in n-octane-α-chloronaphthalene mixed solvents indicate larger inhomogeneous broadening than data for the same molecule in neat α-chloronaphthalene. It is also demonstrated that inhomogeneous broadening can have a drastic effect or excitation profiles in the region of a weakly allowed electron state. This is due to the great sensitivity of interference between resonance and preresonance scattering to the type of line broadening mechanism operative in the system.     

Contributions of symmetric and asymmetric normal coordinates to the intervalence electronic absorption and resonance Raman spectra of a strongly coupled p-phenylenediamine radical cation

Resonance Raman spectroscopy, electronic absorption spectroscopy, and the time-dependent theory of spectroscopy are used to analyze the intervalence electron transfer properties of a strongly delocalized class III molecule, the tetraalkyl-p-phenylene diamine radical cation bis(3-oxo-9-azabicyclo[3.3.1]non-9-yl)benzene ((k33)(2)PD(+)). This molecule is a prototypical system for strongly coupled organic intervalence electron transfer spectroscopy. Resonance Raman excitation profiles in resonance with the lowest energy absorption band are measured. The normal modes of vibration that are most strongly coupled to the intervalence transition are identified and assigned by using UB3LYP/6-31G(d) calculations. Excited state distortions are obtained, and the resonance Raman intensities and excitation profiles are calculated by using the time-dependent theory of Raman spectroscopy. The most highly distorted normal modes are all totally symmetric, but intervalence electron transfer absorption spectra are usually interpreted in terms of a model based on coupling between potential surfaces that are displaced along an asymmetric normal coordinate. This model provides a convenient physical picture for the intervalence compound, but it is inadequate for explaining the spectra. The absorption spectrum arising from only the strongly coupled surfaces consists of a single narrow band, in contrast to the broad, vibronically structured experimental spectrum. The electronic absorption spectrum of (k33)(2)PD(+) is calculated by using exactly the same potential surfaces as those used for the Raman calculations. The importance of symmetric normal coordinates, in addition to the asymmetric coordinate, is discussed. The observed vibronic structure is an example of the missing mode effect; the spacing is interpreted in terms of the time-dependent overlaps in the time domain.     

Raman,resonance Raman and infrared spectra of potassium uranyl croconate

The Raman, resonance Raman and IR spectra of potassium uranyl croconate, UO₂(H₂O)K₂(C₅O₅)₂ were obtained and interpreted. Several croconate modes are split indicating a substantial decrease in the oxocarbon symmetry, as is to be expected from a recent crystallographic investigation, revealing the coordination of the oxocarbon to be two non-equivalent UO²⁺₂ moieties in a monodentate fashion. In terms of vibrational frequency shifts it can be concluded that the UO²⁺₂ moiety behaves as an isolated oscillator.The resonance Raman results suggest that the strong band centered around 450 nm in the UV—vis spectrum should be assigned to a charge transfer transition from the oxocarbon to the uranyl ion. In fact, as resonance is approached, both uranyl and croconate modes are enhanced. It can also be inferred that the chromophore is rather delocalized into the oxocarbon ring, rather than localized in the carbonyl groups as previously observed for other croconate complexes.     

Analytic and numerical approach to multidimensional predissociation and resonance Raman scattering

Scattering theory is used to show that resonance Raman scattering and predissociation probabilities for multidimensional systems can be obtained from numerical solutions of the appropriate scattering coupled equations. Analytic results are presented for two-dimensional systems in terms of Airy functions. These analytic results are used to verify the coupled equations approach. An example is presented for the resonant photon scattering by an electronic state with one bound and one dissociative mode.     

Generalization of Raman intensity expressions so as to include resonance

The existing expressions for Raman intensities are extended to the resonance region. Analytical formulas are obtained in the harmonic oscillator approximation.     

Dynamic electrophoresis of a spherical dispersion of soft particles subject to a stress-jump condition

The dynamic mobility of a spherical dispersion of soft particles, where a particle comprises a rigid core and a membrane layer, is evaluated for the case when the shear stress across the membrane layer-liquid interface is discontinuous, the so-called stress-jump condition. We show that, due to the effect of double-layer deformation, the magnitude of the dynamic mobility of a particle has a local maximum and the corresponding phase angle has a negative (phase lead) local minimum at a low to medium level of the frequency of the applied electric field. This effect becomes insignificant if the frequency of the applied electric field is sufficiently high. The stress-jump condition may lead to a significant influence on the drag, and consequently the mobility of a particle. The degree of influence depends upon the sign of the stress-jump coefficient and the charged conditions of the membrane layer of the particle.     

Electronic and vibrational resonance Raman spectra of octamethyluranocene

The Raman spectrum of bis(tetramethylcyclo-octatetraene)uranium (U(TMCOT)₂), excited in resonance with its visible charge-transfer transitions shows an anomalously polarized electronic band at 473 cm^?1, twice as broad as the analogous band of uranocene, at 466 cm^?1. The broadening is attributed to crystal-field splitting associated with the lowered symmetry introduced by the methyl group, and/or a distribution of rotamer populations. Totally symmetric vibrational modes are observed at 879, 750, 580, 513 and 95 cm^?1; possible assignments are discussed.     

Theory of fluorescence and Raman scattering near resonance

Using a simple model for a molecular system in a bath, the cross section for Raman scattering around resonance is calculated. Without introducing constant relaxation times at the outset, the calculation yields a sharp coherent term, and a broad “hot” luminescence term. The second term is due to dephasing; its relative strength depends on the incident light frequency, and it disappears away from resonance.     

Molecular structure and vibrational spectra of spin-crossover complexes in solution and colloidal media: resonance Raman and time-resolved resonance Raman studies

The spin-crossover system [Fe(btpa)](PF(6))(2) (btpa = N,N,N',N'-tetrakis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) and the predominantly low-spin species [Fe(b(bdpa))](PF(6))(2) ((b(bdpa) = N,N'-bis(benzyl)-N,N'-bis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) have been characterized by means of X-ray diffraction. The unit cell of [Fe(btpa)](PF(6))(2) contains two crystallographically independent molecules revealing octahedral low-spin and quasi-seven-coordinated high-spin structures. The unit cell of [Fe(b(bdpa))](PF(6))(2) contains two crystallographically independent molecules one of which corresponds to a low-spin structure, while the other reveals a disordering. On the basis of magnetic susceptibility and M?ssbauer measurements, it has been proposed that this disorder involves low-spin and high-spin six-coordinated molecules. The structures of [Zn(btpa)](PF(6))(2) and [Ru(btpa)](PF(6))(2) have been determined also. Pulsed laser photoperturbation, coupled here with time-resolved resonance Raman spectroscopy (TR(3)), has been used to investigate, for the first time by this technique, the relaxation dynamics in solution on nanosecond and picosecond time scales of low-spin, LS ((1)A) --> high-spin, HS ((5)T) electronic spin-state crossover in these Fe(II) complexes. For the nanosecond experiments, use of a probe wavelength at 321 nm, falling within the pi-pi transition of the polypyridyl backbone of the ligands, enabled the investigation of vibrational modes of both LS and HS isomers, through coupling to spin-state-dependent angle changes of the backbone. Supplementary investigations of the spin-crossover (SCO) equilibrium in homogeneous solution and in colloidal media assisted the assignment of prominent features in the Raman spectra of the LS and HS isomers. The relaxation data from the nanosecond studies confirm and extend earlier spectrophotometric findings, (Schenker, S.; Stein, P. C.; Wolny, J. A.; Brady, C.; McGarvey, J. J.; Toftlund, H.; Hauser, A. Inorg. Chem. 2001, 40, 134), pointing to biphasic spin-state relaxation in the case of [Fe(btpa)](PF(6))(2) but monophasic in the case of [Fe(b(bdpa))](PF(6))(2). The picosecond results suggest an early process complete in 20 ps or less, which is common to both complexes and possibly includes vibrational relaxation in the initially formed (5)T(2) state.     

Evaluation of alumina slurry dispersion by nuclear magnetic resonance relaxation as a comparison to conventional dispersion evaluation methods

In this paper, we evaluated the particle dispersion degree of alumina slurry containing a dispersant by solvent nuclear magnetic resonance (NMR) relaxation and compared it with conventional dispersion evaluation methods such as viscosity, particle size, and sedimentation height measurements. The dispersion of slurry was evaluated via numerical analysis of the transverse relaxation time (T₂). The effect of the changes in different parameters of the experiment in terms of milling time, solid loading, and dispersant amount was investigated by NMR relaxation as well as conventional methods. The results of NMR relaxation measurements revealed that T₂ correlates well with other dispersion evaluation methods; thus, it is an efficient technique to evaluate the dispersion of alumina slurry, specifically, when studying the effect of the change in milling time and dispersion amount.     

Determination of adrenaline and noradrenaline by resonance Raman spectrometry

Aminochromes of adrenaline and noradrenaline show resonance Raman scattering at 1480 and 1430 cm(-1) respectively, with Ar(+) excitation. Scattering intensity is a linear function of concentration. Detection limits are 1 x 10(-6)M. Both catecholamines can be determined in a single measurement.     

Vibrational analysis of hydroxyflavylium derivatives by IR,Fourier transform Raman and resonance Raman spectroscopies

In order to give a better insight into the vibrational properties of anthocyanins, the synthesis and the vibrational studies of some hydroxyflavylium derivatives with a controlled substitution pattern have been performed. The IR, Raman and resonance Raman spectra of the investigated hydroxyflavylium compounds have been recorded in the solid and solution states. A number of lines have been assigned on the basis of deuterium isotopic shifts, resonance enhancement and previous studies on parent compounds. An attempt has been made to analyze the influence of hydroxy substituents on vibrational properties of the investigated flavylium cations.     

Resonance Raman optical activity and surface enhanced resonance Raman optical activity analysis of cytochrome c

High-resolution resonance Raman (RR) and resonance Raman optical activity (ROA) spectra of cytochrome c were obtained in order to perform full assignment of spectral features of the resonance ROA spectrum. The resonance ROA spectrum of cytochrome c revealed a distinct spectral signature pattern due to resonance enhanced skeletal porphyrin vibrations, more pronounced than any contribution from the protein backbone. Combining the intrinsic resonance properties of cytochrome c with the surface plasmon enhancement achieved with colloidal silver particles, the surface enhanced resonance Raman scattering (SERRS) and surface enhanced resonance ROA (SERROA) spectra of the protein were successfully obtained at concentrations as low as 1 microM. The assignments of spectral features were based on the information obtained from the RR and resonance ROA spectra. Excellent agreement between RR and SERRS spectra is reported, while some disparities were observed between the resonance ROA and SERROA spectra. These differences can be ascribed to perturbations of the physical properties of the protein upon adhesion to the surface of the silver colloids.     

Application of resonance Raman spectrometry to the determination of vitamin B12.

A gel filtration technique is described for the study of the complexation of dissolved metals by humic and fulvic acids. Measurements can be made under realistic conditions of pH and free metal ion concentrations, both of which can be maintained by the use of TRIS as a buffer. The procedure permits the determination not only of the overall stability constant, but of the binding stoichiometries and the intrinsic stability constants associated with the various types of metal binding sites. The procedure has been applied to the investigation of the interaction of fresh-water fulvic acids with Cu, Zn and Ni, and has provided evidence for the existence of two different types of binding sites in the fulvic acid molecule.     

Application of metalloporphyrins and methylviologen-pendent iron porphyrin to reduction of diphenylsulfoxide

In the two-electron reduction of diphenylsulfoxide to diphenylsulfide, which is considered a model reaction of sulfite reduction catalyzed by sulfite reductase, methylviologen-pendent iron(III) porphyrin exhibits much higher catalytic activity than usual iron(III) and manganese(III) tetraphenylporphyrins, while cobalt(II) tetraphenylporphyrin exhibits much less catalytic activity than the others. Discussion about the active species and the reason of the acceleration by methylviologen-pendent is presented.     

An infrared and resonance Raman spectroscopic study of phenylazonaphthol pigments

The IR, resonance Raman (RR) and electronic spectra of two phenylazonaphthol pigments, LRC Scarlet and 4BL Red, have been measured and assignments of the vibrational and electronic spectra were facilitated by ab initio calculation s at the B3-LYP/DZ level. Vibrational spectra indicate that the major species in the solid state are the hydrazo tautomers. Electronic spectra are in accordance with the nature of the electronic transitions predicted by time-dependent B3-LYP/DZ calculations.