Structural, Electronic, and Vibrational Properties of Amino-adamantane and Rimantadine Isomers

We performed a first principles total energy investigation on the structural, electronic, and vibrational propel ties of adamantane molecules, functionalized with amine and ethanamine groups. We computed the vibrational signatures of amantadine and rimanadine isomers with the functional groups bonded to clinic:ill carbon sites By comparing Out results with recent infrared and Raman spectroscopic data, we discuss the possible presence of different isomers in experimental samples.

DFT study of the electronic, vibrational, and optical properties of SnO(2)

We report results on the electronic, vibrational, and optical properties of SnO(2) obtained using first-principles calculations performed within the density functional theory. All the calculated phonon frequencies, real and imaginary parts of complex dielectric function, the energy-loss spectrum, the refractive index, the extinction, and the absorption coefficients show good agreement with experimental results. Based on our calculations, the SnO(2) electron and hole effective masses were found to be strongly anisotropic. The lattice contribution to the low-frequency region of the SnO(2) dielectric function arising from optical phonons was also determined resulting the values of E > (1aSyen) (latt) (0) = 14.6 and E > (1ayen) (latt) (0) = 10.7 for directions perpendicular and parallel to the tetragonal c-axis, respectively. This is in excellent agreement with the available experimental data. After adding the electronic contribution to the lattice contribution, a total average value of E >(1)(0) = 18.2 is predicted for the static permittivity constant of SnO(2).

Furan interaction with the Si(001)-(2 x 2) surface: structural, energetics, and vibrational spectra from first-principles

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of furan on the silicon (001) surface. A direct comparison of different adsorption structures with x-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), high resolution electron energy loss spectroscopy (HREELS), near edge x-ray absorption fine structure (NEXAFS), and high resolution spectroscopy experimental data allows us to identify the [4 + 2] cycloaddition reaction as the most probable adsorbate. In addition, theoretical scanning tunnelling microscopy (STM) images are presented, with a view to contributing to further experimental investigations.

Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.

The intramolecular charge transfer in a donor-pi-acceptor dianion probed by resonance Raman spectroscopy and quantum chemical calculations

The dideprotonation of 4-(4-nitrophenylazo)resorcinol generates an anionic species with substantial electronic pi delocalization. As compared to the parent neutral species, the anionic first excited electronic transition, characterized as an intramolecular charge transfer (ICT) from the CO(-) groups to the NO(2) moiety, shows a drastic red shift of ca. 200 nm in the lambda(max) in the UV-vis spectrum, leading to one of the lowest ICT energies observed (lambda(max) = 630 nm in dimethyl sulfoxide (DMSO)) in this class of push-pull molecular systems. Concomitantly, a threefold increase in the molar absorptivity (epsilon(max)) in comparison to the neutral species is observed. The resonance Raman enhancement profiles reveal that in the neutral species the chromophore involves several modes, as nu(C-N), nu(N=N), nu(C=C) and nu(s)(NO(2)), whereas in the dianion, there is a selective enhancement of the NO(2) vibrational modes. The quantum chemical calculations of the electronic transitions and vibrational wavenumbers led to a consistent analysis of the enhancement patterns observed in the resonance Raman spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

Structural and vibrational characterization of polyaniline nanofibers prepared from interfacial polymerization

This work deals with the structural and vibrational characterization of PANI nanofibers prepared through interfacial polymerization using different concentrations of HCl aqueous solution. The results were compared to those obtained by PANI prepared through the conventional route. X-ray diffraction and small-angle X-ray scattering techniques showed that high concentrations of HCl solutions used in the preparation of the PANI nanofibers reduce their crystallinity. The increase of regions with granular morphology was also observed in the scanning electron microscopy images. The changes in the resonance Raman spectra from 200 to 500 cm(-1), FTIR spectra, and the EPR data of the PANI nanofibers reveal an increase in the torsion angles of C-ring-N-C-ring segments owing the formation of bipolarons in the PANI backbone higher than the PANI samples prepared by conventional route.

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Bichromophoric behavior of nitrophenyl-triazene anions: a resonance Raman spectroscopy investigation

Highly delocalized molecular frameworks with intense charge transfer transitions, known as push-pull systems, are of central interest in many areas of chemistry, as is the case of nitrophenyl-triazene derivatives. The 1,3-bis(2-nitrophenyl)triazene and 1,3-bis(4-nitrophenyl)triazene were investigated by electronic (UV-Vis) and resonance Raman (RR) spectroscopies. The bichromophoric behavior of 1,3-bis(4-nitrophenyl)triazene anion opens the possibility of tuning with visible radiation, two distinct electronic states. The RR profiles of nitrophenyl-triazene derivatives clearly show that the first allowed electronic state can be assigned to a charge transfer from the ring pi system to the NO2 moiety (ca 520 nm), while the second, as a charge transfer from N-3(-) to the aromatic ring (ca 390 nm). In the para-substituted derivative, a more efficient electron transfer and a greater energy separation between the two excited states are observed. Copyright (C) 2008 John Wiley & Sons, Ltd.

Charge-transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E(laser) = 1.17 eV suggest that a charge-transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright (C) 2010 John Wiley & Sons, Ltd.

Deriving the magnitude of niobium off-center displacement in ferroelectric niobates from infrared spectroscopy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural investigations of tungsten silver phosphate glasses by solid state NMR, vibrational and X-ray absorption near edge spectroscopies

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Molecular structures and vibrational frequencies for [PdX2(tdmPz)] (X = Cl-, SCN-): A DFT study

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Vibrational spectra of pilocarpine hydrochloride crystals

Pilocarpine is a natural substance with potential application in the treatment of several diseases. In this work Fourier Transform (FT)-Raman spectrum and the Fourier Transform infra red (FT-IR) spectrum of pilocarpine hydrochloride C11H17N2O2+.Cl- were investigated at 300 K. Vibrational wavenumber and wave vector have been predicted using density functional theory (B3LYP) calculations with the 6-31 G(d,p) basis set. A comparison with experiment allowed us to assign most of the normal modes of the crystal.

Comparative vibrational spectra of pilosine and epiisopilosine crystals

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Vibrational spectra and surface-enhanced resonance Raman scattering of palladium phthalocyanine evaporated films

The vibrational spectra of palladium phthalocyanine (PdPc) evaporated thin solid films are reported, including the resonance Raman scattering, surface-enhanced resonance Raman scattering (SERRS) and SERRS mapping of the film surface using micro-Raman spectroscopy with 633 nm laser radiation. SERRS of PdPc was obtained by evaporating an overlayer of Ag nanoparticles on to the PdPc film on glass. The SERRS enhancement factor is estimated as similar to10(4) with reference to PdPc evaporated films on glass. The molecular organization of the PdPc evaporated films was probed using transmission and reflection-absorption infrared spectra. It was established that a random molecular distribution found in PdPc evaporated films is independent of temperature. No evidence of thermal degradation due to thermal annealing was found in the films. Electronic absorption and emission spectra are also discussed. Copyright (C) 2002 John Wiley Sons, Ltd.