Search results for "Molecular electronic transition"
showing 10 items of 59 documents
Carbonyl-functionalized quaterthiophenes: a study of the vibrational Raman and electronic absorption/emission properties guided by theoretical calcul…
2011
This work investigates the evolution of the molecular, vibrational, and optical properties within a family of carbonyl-functionalized quaterthiophenes: 5,5'''-diheptanoyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'''-diperfluorohexylcarbonyl-2,2':5',2'':5'',2'''-quaterthiophene (2), and 2,7-[bis(5-perfluorohexylcarbonylthien-2-yl)]-4H-cyclopenta[2,1-b:3,4-b']-dithiophene-4-one (3). The analysis is performed by Raman and UV/Vis absorption/excitation/fluorescence spectroscopy in combination with density functional calculations. Theoretical calculations show that substitution with carbonyl groups and perfluorohexyl chains induces progressive quinoidization of the π-conjugated backbone in co…
Phase stability and electronic structure of iridium metal at the megabar range
2019
[EN] The 5d transition metals have attracted specific interest for high-pressure studies due to their extraordinary stability and intriguing electronic properties. In particular, iridium metal has been proposed to exhibit a recently discovered pressure-induced electronic transition, the so-called core-level crossing transition at the lowest pressure among all the 5d transition metals. Here, we report an experimental structural characterization of iridium by x-ray probes sensitive to both long- and short-range order in matter. Synchrotron-based powder x-ray diffraction results highlight a large stability range (up to 1.4 Mbar) of the low-pressure phase. The compressibility behaviour was char…
Vibrational analysis of Ni(II)- and Cu(II)-octamethylchlorin by polarized resonance Raman and Fourier transform infrared spectroscopy
2001
We measured the polarized resonance Raman spectra of Cu(II)-2,2,7,8,12,13,17,18-octamethylchlorin in CS2 at various excitation wavenumbers in a spectral region covering the Qy, Qx and Bx optical absorption bands. Additionally, we measured the FTIR-Raman spectrum of the highly overcrowded spectral region between 1300 and 1450 cm−1. The spectral decomposition was carried out by a self-consistent global fit to all spectra obtained. The thus identified Raman and IR lines were assigned by comparison with the resonance Raman spectra of Cu(II)-octaethylporphyrin, by utilizing their depolarization ratio dispersions and by a normal mode analysis. The latter was based on a modified transferable molec…
Electronic structure of p-type ultraviolet-transparent conducting CuScO2 films
2008
Abstract We investigate the electronic structure of CuScO 2 thin films grown on sapphire and mica substrates by pulsed laser deposition. X-ray diffraction and microanalysis confirm that the films have the expected delafossite crystal structure and stoichiometric proportions. The electronic structure is investigated by means of X-ray and ultraviolet photoelectron spectroscopy. Electronic states in the range 0–1350 eV are identified, making reference to theoretical density-of-states calculations up to 80 eV. Photoelectron spectra near the Fermi energy confirm the p-character of the films. Optical absorption spectroscopy shows that the films are transparent up to 3.7 eV and exhibit an intense …
Intramolecular electronic excitation energy transfer in donor∕acceptor dyads studied by time and frequency resolved single molecule spectroscopy
2008
Electronic excitation energy transfer has been studied by single molecule spectroscopy in donor/acceptor dyads composed of a perylenediimide donor and a terrylenediimide acceptor linked by oligo(phenylene) bridges of two different lengths. For the shorter bridge (three phenylene units) energy is transferred almost quantitatively from the donor to the acceptor, while for the longer bridge (seven phenylene units) energy transfer is less efficient as indicated by the occurrence of donor and acceptor emission. To determine energy transfer rates and efficiencies at the single molecule level, several methods have been employed. These comprise time-correlated single photon counting techniques at r…
Role of vitreous matrix on the optical activity of Ge-doped silica
2003
Abstract We report an experimental study on the relationship between the optical activity of Ge-oxygen deficient centers and dynamic properties and conformational heterogeneity of vitreous matrix in silica. We focus our attention on the absorption band at ∼5.2 eV (B 2β ) and on the two related emissions at ∼4.2 eV (α E ) and at ∼3.1 eV (β). From the temperature dependence of B 2β band we estimate a mean energy value of 26 meV for local vibrational modes coupled to the electronic transition, suggesting that the chromophore and its surrounding have access to low frequency dynamics. From the thermal behavior of the two emissions we distinguish the two competitive relaxation processes from the …
Low temperature optical spectroscopy of low-spin ferric hemeproteins
1996
We report the Soret absorption spectra (500-350 nm) of the cyanomet derivatives of human hemoglobin and horse myoglobin, in the temperature range 300-20 K and in two different solvents (65% v/v glycerol-water or 65% v/v ethylene glycol-water). In order to obtain information on stereodynamic properties of active site of the two hemeproteins, we perform an analysis of the band profiles within the framework of electron-vibrations coupling. This approach enables us to single out the various contributions to the spectral bandwidth, such as those arising from non-radiative decay of the excited electronic state (homogeneous broadening) and from the coupling of the electronic transition i) with hig…
Infrared study of the MoO3 doping efficiency in 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP)
2013
AbstractElectrochemical doping produces clear changes in the vibrational spectra of organic semiconductors as we show here for the system molybdenum oxide (MoO3) doped into the charge transport material 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP). Based on density-functional theory (DFT) calculations of vibrational spectra, the new spectral features can be attributed to the CBP cation that forms as a result of electron transfer from CBP to MoO3. The intensity of the new vibrational lines is a direct measure for the probability of charge transfer. MoO3 agglomerating within the CBP matrix limits the active interface area between the two species. The appearance of a broad electronic transition …
A mutliconfigurational study of low-lying electronic states of KO
1992
Abstract Potential energy curves and spectroscopic parameters of several electronic states of the KO molecule have been calculated using multi-configurational methods. The KO B 2Π state, first time theoretically described, presents a strong avoided crossing with the A 2Π state, and allows for the explanation of the observed fluorescence of the KO molecule. Eleven electronic states have been studied at all the internuclear distances. Effects of complete active space and basis set selections on the results are also analyzed.
Theoretical Study on the Structures and Electronic Spectra of TCNE2−
2006
Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) compiles have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE 2- has D 2d symmetry in vacuum as well as in the solvents dichloromethane and cicetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoreitcal results, are compared to the experimental data and good agreement is achieved.