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Optical Transitions (optical + transition)
Selected AbstractsOxygen induced band-gap reduction in ZnOxSe1,x alloysPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 3 2004W. Shan Abstract The effect of alloying a small amount of ZnO with ZnSe on the electronic band structure has been studied. Optical transitions in MBE-grown ZnOxSe1,x epitaxial films (0 , x , 0.0135) were investigated using photoreflectance and photoluminescence spectroscopies. The fundamental band-gap energy of the alloys was found to decrease at a rate of about 0.1 eV per atomic percent of oxygen. The pressure dependence of the band gap was also found to be strongly affected by the O incorporation. Both effects can be quantitatively explained by an anticrossing interaction between the extended states of the conduction band of ZnSe and the highly localized oxygen states located at approximately 0.22 eV above the conduction band edge. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Reflectance-anisotropy study of the dynamics of molecular beam epitaxy growth of GaAs and InGaAs on GaAs (001)PHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 8 2008J. Ortega-Gallegos Abstract Reflectance-Anisotropy (RA) observations during the Molecular Beam Epitaxy (MBE) growth of zincblende semiconductors films were carried out using the E1 optical transition as a probe. We follow the kinetics of the deposition of GaAs and In0.3Ga0.7As on GaAs (001) at growth rates of 0.2 and 0.25 ML/s, respectively. During growth we used a constant As4 or As2 flux pressure of 5× 10,6 Torr. Clear RA-oscillations were observed during growth with a period that nearly coincides with the growth period for a Ga-As bilayer. RHEED was used as an auxiliary technique in order to obtain a correlation between RHEED and RA oscillations. On the basis of our results, we argue that RAS oscillations are mainly associated to periodic changes in surface atomic structure. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] UV Polymerisation of Surfactants Adsorbed at the Nematic Liquid Crystal,Water Interface Produces an Optical ResponseCHEMPHYSCHEM, Issue 17 2009Paul D. I. Fletcher Prof. Abstract We have investigated the changes in crossed polariser optical textures produced by adsorption and UV polymerisation of a range of polymerisable surfactants at the interface between a nematic liquid crystal and water. Similar to non-polymerisable surfactants, the adsorption of polymerisable surfactants with sufficiently long hydrophobic tail groups produces a transition from planar to homeotropic anchoring. UV polymerisation of surfactants with a polymerisable group located in the hydrophobic tail region changes the anchoring from homeotropic back to planar. Polymerisation in the hydrophilic headgroup region does not produce an optical transition. We demonstrate that these systems can be used to "write with light" in the interfaces and that they form the basis of a UV sensor device in which the optical response is visible to the naked eye. [source] Spin-Based Optical Quantum Information ProcessingISRAEL JOURNAL OF CHEMISTRY, Issue 4 2006Ehoud Pazy We shall present a review of semiconductor spin-based implementation schemes for the realization of quantum information/computation solid-state devices. After briefly describing the fundamentals of quantum computation theory, we shall introduce and discuss potential implementation schemes based on the spin degrees of freedom in semiconductor nanostructures. More specifically, we shall describe an implementation scheme for quantum information processing in which the spin degrees of freedom of electrons confined to a quantum dot are the computational degrees of freedom, and spins are manipulated/controlled through interaction between trionic states created by interband optical transitions by ultrafast sequences of multicolor laser pulses. We will also review briefly an adiabatic method for operating the two-qubit gate that avoids the main imperfections present in real quantum dots: exciton decay, hole mixing, and phonon decoherence. [source] Excited states of OsO4: A comprehensive time-dependent relativistic density functional theory studyJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 3 2010Yong Zhang Abstract A large number of scalar as well as spinor excited states of OsO4, in the experimentally accessible energy range of 3,11 eV, have been captured by time-dependent relativistic density functional linear response theory based on an exact two-component Hamiltonian resulting from the symmetrized elimination of the small component. The results are grossly in good agreement with those by the singles and doubles coupled-cluster linear response theory in conjunction with relativistic effective core potentials. The simulated-excitation spectrum is also in line with the available experiment. Furthermore, combined with detailed analysis of the excited states, the nature of the observed optical transitions is clearly elucidated. It is found that a few scalar states of 3T1 and 3T2 symmetries are split significantly by the spin-orbit coupling. The possible source for the substantial spin-orbit splittings of ligand molecular orbitals is carefully examined, leading to a new interpretation on the primary valence photoelectron ionization spectrum of OsO4. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] Optical properties of InN grown on Si(111) substratePHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 5 2010E. Sakalauskas Abstract A comprehensive characterization of the optical properties of wurtzite InN films grown by molecular beam epitaxy on Si(111) substrates is presented. Two types of films are investigated in this work: InN on AlN/Si(111) and InN on GaN/AlN/Si(111). Their properties are compared to a layer deposited on GaN/sapphire substrate. The dielectric function (DF) is obtained from spectroscopic ellipsometry (SE). The infrared studies yield the plasma frequency and thus the electron density, while the interband absorption is probed between 0.56 and 9.8,eV. For InN grown on Si(111) substrate, the absorption onset is slightly shifted to higher energies with respect to the InN film grown on GaN/sapphire which can be attributed to higher electron concentrations. Despite this, strongly pronounced optical transitions due to critical points of the band structure are found in the high-energy part of the DF. It emphasizes the already promising quality of the InN films on silicon. Band-gap renormalization (BGR), band filling, and strain are taken into account in order to estimate the intrinsic band gap of wurtzite InN. For the InN layers on silicon, we get a band gap between 0.66 and 0.685,eV. [source] Crystallization behavior of Sb70Te30 and Ag3In5Sb60Te32 chalcogenide materials for optical media applicationsPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 2 2008M. L. Lee Abstract Addition of In and Ag into eutectic Sb70Te30 fast-growth material was studied. We explored the optical transitions and crystallization kinetics of Sb70Te30 and Ag3In5Sb60Te32 recording films. The results showed that Ag3In5Sb60Te32 has a higher crystallization temperature but a similar melting point compared to Sb70Te30. In both the crystalline and amorphous states, addition of Ag and In increased the refractive index and decreased the extinction coefficient of Sb70Te30. Ag3In5Sb60Te32 has better thermal stability and a lower crystallization speed than Sb70Te30 film. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Optical, structural, and magnetic properties of p-type GaN implanted with Fe+ (5 and 10 at%)PHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 1 2007Yoon Shon Abstract p-type GaN epilayers were prepared by metalorganic chemical vapor deposition and subsequently implanted with Fe+. The results of energy dispersive X-ray peak displayed the Fe-injected concentration of 5 and 10 at%, respectively. The results of photoluminescence measurement show that optical transitions related to Fe appear at 2.5 and 3.1 eV. It was confirmed that the photoluminescence peak at 2.5 eV is a donor-Fe acceptor transition and the photoluminescence peak at 3.1 eV is a conduction band-Fe acceptor transition. Apparent ferromagnetic hysteresis loops measured at 10 and 300 K with the Fe concentration of 10 at% were observed, and the temperature-dependent magnetization displayed a ferromagnetic behavior persisting up to 300 K. The systematic enhancement of ferromagnetic hysteresis loops for GaN implanted with high doses of Fe (5 , 10 at%) takes place with an increase in the annealing temperature from 700 to 850 °C. The trends of magnetic properties coincide with the results of the increased full width at half maximum of triple axis diffraction for GaN (0002) including the appearance of GaFeN, the enhanced Fe-related photoluminescence transitions, and the increased sizes of symmetric spin ferromagnetic domains GaFeN in atomic force microscopy and magnetic force microscopy systematically. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Influence of the annealing temperature on the optical transitions of InGaAsP-based quantum well structures investigated by photoreflectance spectroscopyPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 7 2005A. Podhorodecki Abstract Photoreflectance (PR) and photoluminescence (PL) spectroscopies have been used to study the effect of the rapid thermal annealing (RTA) on InGaAsP-based quantum wells (QWs) which are the active part of a laser structure tailored at 1.5 µm. In the case of PL, it has been observed that the RTA enhances PL intensity and tunes the emission wavelength of the laser structure to blue. In case of PR due to its absorption character, we were able to study QW transitions related to excited states, besides the fundamental transition observed in PL. In addition, optical transitions related to other part of the laser structure have been observed in PR. It has been shown that there exists a "critical" annealing temperature (720 °C) where the energy shift appears. We have observed a blueshift for both the ground and excited state transitions, but in the case of the ground state transitions the blueshift has been found to be bigger. The magnitude of this blueshift has been found to change linearly from 0 to ,15 meV with the rise of temperature from 720 to 780 °C. Below 720 °C no significant change in the energy of the QW transitions is observed. In the case of PR transitions related to the other part of the laser structure, i.e., the quaternary InGaAsP barriers, it has been observed that after annealing PR features associated with these layers rather do not shift, they change only their line-shape. Also, it has been shown that RTA does not destroy the optical quality of the samples. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Effect of electric field on the probability of optical transitions in InGaAs/GaAs quantum wells observed by photo- and electroreflectance methodsPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 7 2005A. N. Pikhtin Abstract The influence of an electric field on the energy spectrum and the probability of optical transitions in InGaAs/GaAs single quantum wells (QWs) of different widths has been investigated with photo- and electroreflectance techniques. The electric field in the area of a QW is varied in a wide range and controlled by well-defined Franz,Keldysh oscillations. A quadratic red shift of electroreflectance features concerned with interband excitonic transitions in QWs is observed. The electric field dependence of the intensity of these features and calculated data for the probability of optical transitions are compared. There are some field values when transitions that are symmetry-forbidden in zero field are much stronger than symmetry-allowed transitions. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Multiphonon processes in impurity centres: nonperturbative theoryPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 2 2005V. Hizhnyakov Abstract A nonperturbative theory of the multiphonon relaxation of a strongly excited local vibration is developed. It is found that for a high initial level, the relaxation first accelerates in time, and later starts to slow down. The experimental evidence of such a non-monotonous relaxation is given by the hot luminescence in solid Xe. A theory of optical transitions in a center with strongly reduced local springs in the final electronic state is also developed. In this case a resonant increase of the local density of states of low-frequency phonons takes place, and a low frequency pseudo-local mode emerges. Appearance of such a mode in the final state means that a strong mode mixing takes place at the transition. This results in strong increase of the mean number of created low-frequency phonons. As a consequence, the zero-phonon transition practically disappears and the long-wave part of the phonon sideband is strongly enhanced, resulting in formation of so-called lambda-shaped spectrum. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Effect of composition on the optical properties of the quaternary CuxAg1,xInTe2 thin filmsPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 1 2003E. A. El-Sayad Abstract Thin films of CuxAg1,xInTe2 solid solutions (x = 0.25, 0.50 and 0.75) were deposited by thermal evaporation of prereacted materials on glass substrates. X-ray diffraction (XRD) studies has revealed that the as-deposited and thermally annealed films are polycrystalline with single-phase of a tetragonal chalcopyrite structure as that of bulk material with (112) predominant reflecting plane. The films compositions were confirmed by using energy dispersive analysis of X-rays (EDAX). The refractive index, n, and the extinction coefficient, k, of the annealed films with different compositions were determined in the spectral range, 400,2500 nm. Three characteristic energy gaps have been determined from the analysis of optical absorption spectrum for each composition. The three energy gaps are attributed to the optical transitions from the valence sub-bands to the conduction band minimum. Besides, a fourth energy gap has also been obtained for each composition, which may be attributed to the transition from the copper 3d-level to the conduction band minimum. However, the band gaps showed linear variation with the value of x. [source] Theoretical resonant Raman spectra of nanotube (7,0) with point defectsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 11-12 2009Valentin N. Popov Abstract The Raman spectra of the nanotube (7,0) with point defects (monovacancy, divacancy, and Stone,Wales defect) were simulated in order to derive spectroscopic signatures of defective nanotubes. First, we calculated the electronic band structure and the phonon dispersion of the defective nanotubes using supercells within a non-orthogonal tight-binding model. We found that new optical transitions and Raman-active phonons appeared in comparison with the perfect nanotube. Secondly, we calculated the resonance Raman excitation profile for all Raman-active phonons of the defective nanotubes and simulated their Raman spectra at specific laser excitation energies. The predicted high-intensity Raman lines can be used as spectroscopic signatures of the defective nanotubes. [source] Theoretical studies of the spin Hamiltonian parameters and the local structure for the orthorhombic V4+ in CaYAlO4PHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 6 2008Chuan-Ji Fu Abstract The spin Hamiltonian parameters (g -factors and the hyperfine structure constants) and the local structure for the orthorhombic V4+ in CaYAlO4 are theoretically studied from the perturbation formulas of these parameters for a 3d1 ion in orthorhombically distorted octahedra. Based on the present studies, this center is explicitly assigned to V4+ occupying the Al3+ site, associated with one next-nearest-neighbor Mg2+ replacing the host Al3+ (i.e. MgAl) in the ab -plane due to the charge compensation. Since the effective charge of the compensator is negative (,e), the ligand O2, intervening in the impurity V4+ and the MgAl would undergo a small displacement (,0.08 Ĺ) towards the central ion because of the electrostatic repulsion. The local structure of this center can be described as elongation of the oxygen octahedron along the c- axis and the slight orthorhombic distortion in the perpendicular direction. The theoretical spin Hamiltonian parameters and the optical transitions based on the above local structure show reasonable agreement with the experimental data. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] First and second optical transitions in single-walled carbon nanotubes: a resonant Raman studyPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 11 2007H. Telg Abstract Resonant Raman spectroscopy was performed to study electron,phonon coupling in single-walled carbon nanotubes separated in solution. By varying the excitation energy from 1.26 eV to 1.93 eV we obtained radial breathing mode resonance profiles of the first and second optical transitions E11 and E22 of the (9,1) and (8,3) tubes. We observe up to 16 times stronger Raman intensities for the E11 transitions which can mostly be attributed to a two times broader linewidth of the E22 transition. Comparison of the matrix element ratio ,11/,22 to theoretical predictions on the electron,phonon coupling show a deviation of a factor 1.7 which might be associated with the change of the exciton,photon matrix element. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Raman intensities of the first optical transitions in carbon nanotubesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 13 2006H. Telg Abstract We performed resonant Raman spectroscopy on the lowest optical transition ES11 of separated single-walled carbon nanotubes by studying the radial-breathing mode (RBM) spectra for excitation energies between 1.15 and 1.48 eV. We were able to extend the experimental Kataura plot to these energies by adding the ES11 transition energies of 11 nanotube chiralities. We discuss also the relative Raman intensities; they are more similar for different family index , than those of the corresponding transitions of the ES22 [1]. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Symmetry of electron states and optical transitions in GaN/AlN hexagonal quantum dotsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 13 2004P. Tronc Abstract The exact symmetry of hexagonal quantum dots (QDs) made of materials with the wurtzite structure such as GaN/AlN QDs for example, is described by the C3v point group and does not depend on the existence of a wetting layer. We have determined the possible exact symmetries of electron states and vibration modes in the dots and derived the optical selection rules. The vibration modes involved in the Frölich interaction are totally symmetric with respect to the C3v group and can induce transitions only between states with the same symmetry. The not totally symmetric modes provide other channels for lowering the energy of excited carriers and excitons by connecting states with symmetries different one from another. The rapid decay of created polarons, due to the short lifetime of vibration modes, releases the carriers and excitons into ground levels. In the envelope function approximation (EFA), the symmetry of the dots is represented by the C6v point group. Interband transitions are allowed only between states whose envelope functions have the same symmetry. EFA artificially increases the number of dark exciton symmetries. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Contactless electroreflectance studies of II,VI nanostructures grown by molecular beam epitaxyPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 3 2004Martín Muńoz Abstract The interband transitions of a single quantum well structure of Zn0.53Cd0.47Se/Zn0.27Cd0.23Mg0.50Se, lattice matched to InP, and of a capped CdSe quantum dot structure have been investigated using contactless electroreflectance. From a comparison of the quantum well optical transitions with those calculated using the envelope function approximation we determined the band offsets for this system. The electroreflectance spectrum of the quantum dot structure shows transitions originating from all the portions of the sample including the quantum dots and the wetting layer. Assuming a lens shape geometry and that the effective height-to-radius ratio observed in uncapped quantum dots is preserved, the size of the capped quantum dots was determined using the observed electroreflectance transitions, and the effective mass approximation. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Contactless electroreflectance and photoluminescence of InAs quantum dots with GaInNAs barriers grown on GaAs substratePHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 2 2007M. Motyka Abstract InAs quantum dots (QDs) with GaInNAs barriers grown on (001) GaAs substrate by molecular beam epitaxy have been studied by contactless electroreflectance (CER) and photoluminescence (PL) spectroscopies. It has been observed that the overgrowth of self-organized InAs QDs with GaInNAs layers effectively tunes the QD emission to the 1.3 ,m spectral region. In case of PL spectra only one peak related to QD emission has been observed. In the case of CER spectra, in addition to a CER feature corresponding to the QD ground state, a rich spectrum of CER resonances related to optical transitions in InAs/GaInNAs/GaAs QW has been observed. It has been concluded that the application of GaInNAs instead InGaAs leads to better control of emission wavelength from InAs QDs since strains in GaInNAs can be tuned from compressive to tensile. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Photoreflectance investigations of energy level structure of InAs quantum dashes embedded in InGaAs/InGaAlAs quantum well grown on InP substratePHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 11 2006W. Rudno-Rudzi Abstract Photoreflectance (PR) and photoluminescence measurements have been performed on molecular beam epitaxy grown InAs quantum dashes (QDash) of various sizes, embedded in In0.53Ga0.47As/In0.53Ga0.23Al0.24As quantum well (QW), grown on InP substrate. PR response from all relevant parts of the structure, i.e InAs/In0.53Ga0.47As QDashes, InAs/In0.53Ga0.47As/In0.53Ga0.23Al0.24As QW, and In0.53Ga0.23Al0.24As barriers, has been obtained. The lowest energy transition related to the ground state transition in QDashes shifts towards red with the increase in QDash sizes (amount of deposited InAs material) reaching wavelengths longer than for structures without the intermediate QW. The experimental data on the energies of optical transitions combined with the numerical calculation within the effective mass approximation has allowed determining the energy level structure of the entire system, including the values of conduction band offset between InGaAs and InGaAlAs layers. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Temperature dependence of 2DEG and excitonic optical transitions in AlGaN/GaN heterostructures on SiCPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 7 2005C. W. Litton Abstract Four (4) unique optical transitions are reported in both the emission and reflection spectra of high-quality AlGaN/GaN heterostructures. Study of the shifts of spectral peak energies and their intensity variations with temperature, reveal that these transitions arise from Free Exciton recombination and transitions between the A- and B-valence bands and the excited states of the 2-dimensional electron gas (2DEG) at the heterointerface. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Effect of adsorption of electronegative and electropositive elements on the surface optical anisotropy of GaAs(001)PHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 8 2003C. Hogan Abstract Surface optical anisotropy of GaAs(001) is extremely sensitive to adsorption of electropositive and electronegative atoms. The oxygen-induced experimental changes of the reflectance anisotropy spectrum of the As-rich (2 × 4) surface are interpreted using ab initio calculations. We conclude that oxygen adsorption, contrary to previous beliefs, does not quench all surface-related optical transitions, but only those for which the initial state is surface-related. Alkali metal (AM) adsorption is found to induce a strong negative signal in the 3.5 eV,5 eV range, weakly dependent on surface reconstruction and AM nature, whose origin is discussed. (© 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Optical spectra of quantum dots: effects of non-adiabaticityPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 4 2003J. T. Devreese Abstract It is shown that in many cases an adequate description of optical spectra of semiconductor quantum dots requires a treatment beyond the commonly used adiabatic approximation. We have developed a theory of phonon-assisted optical transitions in semiconductor quantum dots, which takes into account non-adiabaticity of the exciton,phonon system. Effects of non-adiabaticity lead to a mixing of different exciton and phonon states that provides a key to the understanding of surprisingly high intensities of phonon satellites observed in photoluminescence spectra of quantum dots. A breakdown of the adiabatic approximation gives an explanation also for discrepancies between the serial law, observed in multi-phonon optical spectra of some quantum dots, and the Franck,Condon progression, prescribed by the adiabatic approach. [source] Electronic structure and transport properties of quantum dotsANNALEN DER PHYSIK, Issue 5 2004M. Tews Abstract The subject of this paper are electronic properties of isolated quantum dots as well as transport properties of quantum dots coupled to two electronic reservoirs. Thereby special focus is put on the effects of Coulomb interaction and possible correlations in the quantum dot states. First, the regime of sequential tunneling to the reservoirs is investigated. It is shown that in case degenerate states participate in transport, the resonance positions in the differential conductance generally depend on temperature and the degree of degeneracy. This effect can be used to directly probe degeneracies in a quantum dot spectrum. A further effect, characteristic for sequential tunneling events, is the complete blocking of individual channels for transport. A generalisation of the well known spin blockade is found for correlated dot states transitions through which are not directly spin-forbidden. In the second part, the electronic structure of spherical quantum dots is calculated. In order to account for correlation effects, the few-particle Schrödinger equation is solved by an exact diagonalization procedure. The calculated electronic structure compares to experimental findings obtained on colloidal semiconductor nanocrystals by Scanning Tunneling Spectroscopy. It is found that the electric field induced by the tunneling tip is gives rise to a Stark effect which can break the spherical symmetry of the electronic ground state density which is in agreement with wave-function mapping experiments. The symmetry breaking depends on the competition between exchange energy and the Stark energy. Moreover, a systematic dependence on particle number is found for the excitation energies of optical transitions which explains recent experimental findings on self-organized quantum dots. In the last part, co-tunneling in the Coulomb blockade regime is studied. For this end the tunneling current is calculated up to the forth order perturbation theory in the tunnel coupling by a real-time Green's function approach for the non-equilibrium case. The differential conductance calculated for a quantum dot containing up to two interacting electrons shows complex signatures of the excitation spectrum which are explained by a combination of co-tunneling and sequential tunneling processes. Thereby the calculations show a peak structure within the Coulomb blockade regime which has also been observed in experiment. [source] Radical Ions from 3,3,,,,3,,,,-Tris(butylsulfanyl)-2,2,:5,,2,:5,,2,,,,5,,,,2,,,,:5,,,,,2,,,,-sexithiophene: An Experimental and Theoretical Study of the p - and n -Doped OligomerCHEMPHYSCHEM, Issue 11 2003Angelo Alberti Dr. Abstract The 3,3,,,,3,,,,-tris(butylsulfanyl)-2,2,:5,,2,:5,,2,,,,5,,,,2,,,,:5,,,,,2,,,,-sexithiophene 1 was investigated through spectroscopic (NMR, EPR, UV/Vis-NIR), electrochemical, spectroelectrochemical and theoretical (DFT) studies. The charged species obtained upon its oxidation and reduction were characterised, showing that 1 can exist in at least five different oxidation states, that is, a neutral species, a radical cation, a dication, a radical anion, and a dianion. The long term stability of the radical cation 1+. was evidenced by the 1H NMR study in the presence of small quantities of trifluoroacetic acid (TFA). This approach allowed a comparison of the relative broadening of proton signals of 1, induced by the electron exchange process with traces of radical cation 1+., and the hfc (hyperfine coupling) constants obtained from the EPR study and DFT calculations. In the radical cation, all of the heterocyclic sulphur atoms are not significantly involved in the delocalisation of the unpaired electron, whereas the opposite holds for the radical anion. Time-dependent DFT calculations reproduced well the wavelengths of the optical transitions observed in the spectroelectrochemical experiments for all the five oxidation states and support the formation of the dianion 12,. [source] Ionic Liquid for in situ Vis/NIR and Raman Spectroelectrochemistry: Doping of Carbon NanostructuresCHEMPHYSCHEM, Issue 9 2003Ladislav Kavan Prof. Dr. Abstract 1-butyl-3-methylimidazolium tetrafluoroborate (an ionic liquid) is an advantageous electrolyte for the study of charge-transfer reactions at single-walled carbon nanotubes (SWCNTs) and fullerene peapods (C60@SWCNT). Compared to traditional electrolyte solutions, this medium offers a broader window of electrochemical potentials to be applied, and favorable optical properties for in situ Vis/NIR and Raman spectroelectrochemistry of nano-carbon species. The electrochemistry of both nanotubes and peapods is dominated by their capacitive double-layer charging. Vis/NIR spectroelectrochemistry confirms the charging-induced bleaching of transitions between Van Hove singularities. At high positive potentials, new optical transitions were activated in partly filled valence band. The bleaching of optical transitions is mirrored by the quenching of resonance Raman scattering in the region of tube-related modes. The Raman frequency of the tangential displacement mode of SWCNT shifts to blue upon both anodic and cathodic charging in the ionic liquid. The Raman modes of intratubular C60 exhibit a considerable intensity increase upon anodic doping of peapods. [source] | |||||||||||||