Search results for "Electronic transition"
showing 10 items of 61 documents
Photophysical behavior of norharmane related to proximity effect
1990
Abstract Solvent and temperature effects of fluorescence and its polarization characteristics for norharmane were studied. From the results obtained it is concluded that the fluorescent state changes from the φφ ∗ -type in a polar solvent (EPA) to nφ ∗ -type in a nonpolar solvent (MC), and also that lowest singlet excited states (φφ ∗ -type and nφ ∗ -type) interact by vibronic coupling. In the nonpolar solvent (MC) the lowest singlet excited states are very close in energy and consequently the vibronic coupling is stronger. At high temperatures, in a nonpolar solvent (MC), the emission is from both the φφ ∗ - and nφ ∗ -states due to thermal equilibration, while at low temperatures the emiss…
Alternating, all-trans polyenynes: Model compounds for poly(diacetylene)s with defined conjugation length
1994
The syntheses of polyenynes as model compounds for poly(diacetylene)s (PDAs) are described. Variation of properties (UV–VIS, Raman, NMR and bond geometries) as a function of the chain length was investigated. After extrapolation to infinite chain length these data were compared to those for PDAs. From UV–VIS spectra a value of λ = 551 nm (2.25 eV) was calculated corresponding to the electronic transition of a single polyenyne chain. This energy is located at the low energy end of a yellow PDA solution spectrum. From Raman scattering v(CC) = 2108–2128 cm−1 and v(CC) = 1505–1532 cm−1 were calculated after extrapolation. Similarly sp-C13C NMR data yielded a shift of δ = 100 ppm. These data are…
Transition probabilities of PrII-lines emitted from a ferroelectric plasma source
1991
Abstract An argon-praseodymium plasma was generated under atmospheric pressure between a ceramic ferroelectric plate and a praseodymium plate. The system of plates was connected to an acoustic frequency supply. The plasma radiation was analyzed in the spectral range from 2000 to 7000 A by using a grating spectrograph with a linear dispersion near 1 mm/A, adopted to photoelectric measurements. The emission spectrum of praseodymium was recorded and the intensities of a few hundred lines were measured. Transition probabilities were determined for 62PrII-lines, using available lifetime data for excited levels and measured branching ratios of the corresponding lines. Reasonable agreement has bee…
Facile approaches to build ordered amphiphilic tris(phthalocyaninato) europium triple-decker complex thin films and their comparative performances in…
2010
Solution processed thin films of an amphiphilic tris(phthalocyaninato) rare earth triple-decker complex, Eu(2)[Pc(15C5)(4)](2)[Pc(OC(10)H(21))(8)], have been prepared from three different methods: self-assembly (SA) annealed in solvent vapor, quasi-Langmuir-Shäfer (QLS) and drop casting methods. In particular, we successfully developed a simple QLS process for fabricating ordered multilayers with a good thickness control. The films prepared from three different methods were characterized by a wide range of methods including electronic absorption spectra, IR, X-ray diffraction, atomic force microscopy (AFM), and current-voltage (I-V) measurements. J-type aggregates have been formed with the …
Transition Dipole Orientation of Linear Polyenes: Semiempirical Models and Extrapolation to the Infinite Chain Limit
1999
Linear conjugated polyenes have an electronic transition dipole moment for the strongly allowed 1Ag to 1Bu electronic excitation that is not oriented along the major axis of the polyene chain. In this paper, the experimental values of this off-axis angle are compared to semiempirical and ab initio theoretical predictions. The semiempirical computations are shown to be reliable and are extended to long chains (n = 20). The results are then extrapolated to the infinite chain limit. A nonzero value of 6°−11° for the infinite polyene is suggested by this extrapolation but state of the art ab initio results for a series of small polyenes yield a zero asymptotic value.
Vibrational properties of the surface-nonbridging oxygen in silica nanoparticles
2008
By studying the site-selective luminescence spectra of oxidized silica nanoparticles we identify the electronic and the vibrational lines associated with the surface nonbridging oxygen, $\ensuremath{\equiv}{\text{Si-O}}^{\ifmmode\bullet\else\textbullet\fi{}}$. This defect emits a zero-phonon line inhomogeneously distributed around 2.0 eV with full width at half maximum of 0.04 eV, weakly coupled with the local ${\text{Si-O}}^{\ifmmode\bullet\else\textbullet\fi{}}$ stretching mode whose frequency is measured to be $920\text{ }{\text{cm}}^{\ensuremath{-}1}$. These findings are different from those of the well-characterized defect in the bulk silica thus evidencing structural peculiarities of …
A theoretical study of the rotational structure of the ϵ(0,0) band of NO
2009
This study has been focused on the ϵ(0,0) band of the nitric oxide molecule, associated with the absorption electronic transition D2Σ+X 2Π, in the energetic vacuum ultraviolet region. A temperature of 295 K has been considered. The Molecular Quantum Defect Orbital (MQDO) methodology, with which reliable spectroscopic data have been reached in the γ(0,0), δ(0,0), and δ(1,0) bands of the same molecule, has also been used for these calculations. We hope that the present results might be of straightforward use in atmospheric and interstellar chemistry. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010
A theoretical study of the electronic spectrum of thiophene
1993
Abstract The electronic spectrum of thiophene has been studied using multiconfiguration second-order perturbation theory and extended ANO basis sets. The calculations comprise four singlet valence excited states and the 3s3p3rd Rydberg series. The lowest triplet states were included and some n-π* and n-σ* states. The results have been used to assign the experimental spectrum below 8.0 eV, with a maximum deviation of about 0.1 eV for vertical transition energies. The calculations place the 2 1A1 valence state at 5.33 eV, below the 1 1B2 valence state at 5.72 eV, and the most intense valence transitions at 6.69 eV (3 1A1) and 7.32 eV (4 1B2) with oscillator strengths 0.19 and 0.39, respective…
Protein dynamics: conformational disorder, vibrational coupling and anharmonicity in deoxy-hemoglobin and myoglobin.
1993
In this work we study the temperature dependence of the Soret band lineshape of deoxymyoglobin and deoxyhemoglobin, in the range 300-20 K. To fit the measured spectra we use an approach originally proposed by Champion and coworkers (Srajer et al. 1986; Srajer and Champion 1991). The band profile is modelled as a Voigt function that accounts for the coupling with low frequency vibrational modes, whereas the coupling with high frequency modes is responsible for the vibronic structure of the spectra. Moreover, owing to the position of the iron atom out of the mean heme plane, inhomogeneous broadening brings about a non-Gaussian distribution of 0-0 electronic transition frequencies. The reporte…
Dynamic properties of some β-chain mutant hemoglobins
1995
The thermal behavior of the Soret band relative to the carbonmonoxy derivatives of some beta-chain mutant hemoglobins is studied in the temperature range 300-10 K and compared to that of wild-type carbonmonoxy hemoglobin. The band profile at various temperatures is modeled as a Voigt function that accounts for homogeneous broadening and for the coupling with high- and low-frequency vibrational modes, while inhomogeneous broadening is taken into account with a gaussian distribution of purely electronic transition frequencies. The various contributions to the over-all bandwidth are singled out with this analysis and their temperature dependence, in turn, gives information on structural and dy…