Correlations between frequency of infra-red active vibrational modes and copper-oxygen distance in copper oxides. Application to superconductors

The infra-red spectra of a large number of ternary Cu(II) oxides with at least a quasi square-planar coordination of oxygen around the copper ions have been studied. The frequency of the bands with the highest frequency,v max, is found to correlate extremely well with the shortest Cu–O distance.v max increases at an impressive rate of sim20 cm–1 per 0.01 Å when the Cu–O distance becomes less than 1.97 Å, which is the Cu2+–O2– distance in square-planar CuO4 complexes as obtained from empirical ionic radii considerations. The marked sensitivity may be used as a ldquotitrationrdquo procedure not only to assign bands but also to obtain diagnostic information about local coordination in compounds derived, for example, from the YBa2Cu3O7–d structure such as LaCaBaCu3O7–d . The only example where this correlation fails is in the two-layer non-superconducting oxides derived from La2(Ca, Sr)Cu2O6. The significance of this result is discussed. The marked dependence of frequency on the bond-distance is qualitatively examined in terms of an increased electron-phonon coupling to account for the observed tendency of the superconducting transition temperature to go through a maximum as the average basal plane Cu–O distance is decreased.

Electron transfer reaction in the marcus inverted region: role of high frequency vibrational modes

A theoretical study of the dynamics of photo-electron transfer reactions in the Marcus inverted regime is presented. This study is motivated partly by the recent proposal of Barbara et al. (J. Phys. Chem. 96, 3728, 1991) that a minimal model of an electron transfer reaction should consist of a polar solvent mode (X), a low frequency vibrational mode (Q) and one high frequency mode (q). Interplay between these modes may be responsible for the crossover observed in the dynamics from a solvent controlled to a vibrational controlled electron transfer. The following results have been obtained. (i) In the case of slowly relaxing solvents, the proximity of the point of excitation to an effective sink on the excited surface is critical in determining the decay of the reactant population. This is because the Franck-Condon overlap between the reactant ground and the product excited states decreases rapidly with increase in the quantum number of the product vibrational state. (ii) Non-exponential solvation dynamics has an important effect in determining the rates of electron transfer. Especially, a biphasic solvation and a large coupling between the reactant and the product states both may be needed to explain the experimental results. ©1996 American Institute of Physics

A lattice dynamical treatment for the total potential energy of single-walled carbon nanotubes and its applications: relaxed equilibrium structure, elastic properties, and vibrational modes of ultra-narrow tubes

In this paper, we propose a lattice dynamic treatment for the total potential energy of single-walled carbon nanotubes (SWCNTs) which is, apart from a parameter for the nonlinear effects, extracted from the vibrational energy of the planar graphene sheet. The energetics, elasticity and lattice dynamics are treated in terms of the same set of force constants, independently of the tube structures. Based upon this proposal, we have investigated systematically the relaxed lattice configuration for narrow SWCNTs, the strain energy, the Young's modulus and Poisson ratio, and the lattice vibrational properties with respect to the relaxed equilibrium tubule structure. Our calculated results for various physical quantities are nicely in consistency with existing experimental measurements. In particular, we verified that the relaxation effect makes the bond length longer and the frequencies of various optical vibrational modes softer. Our calculation provides evidence that the Young's modulus of an armchair tube exceeds that of the planar graphene sheet, and that the large diameter limits of the Young's modulus and Poisson ratio are in agreement with the experimental values of graphite; the calculated radial breathing modes for ultra-narrow tubes with diameters ranging between 2 and 5 angstrom coincide with the experimental results and the existing ab initio calculations with satisfaction. For narrow tubes with a diameter of 20 angstrom, the calculated frequencies of optical modes in the tubule's tangential plane, as well as those of radial breathing modes, are also in good agreement with the experimental measurements. In addition, our calculation shows that various physical quantities of relaxed SWCNTs can actually be expanded in terms of the chiral angle defined for the corresponding ideal SWCNTs.

Raman scattering study on vibrational modes in Ga1-xMnxN prepared by Mn-ion implantation

Raman scattering measurements have been carried out on ferromagnetic semiconductor Ga1-xMnxN prepared by Mn-ion implantation and post annealing. The Raman results obtained from the annealed and un-annealed Ga1-xMnxN demonstrate that crystalline quality has been improved in Ga1-xMnxN after annealing. Some new vibrational modes in addition to GaN-like modes are found in the Raman spectra measured from the Ga1-xMnxN where the GaN-like modes are found to be shifted in the higher frequency side than those measured from the bulk GaN. A new vibrational mode observed is assigned to MnN-like mode. Other new phonon modes observed are assigned to disorder-activated modes and Mn-related vibrational modes caused by Mn-ion implantation and post-annealing. (c) 2006 Elsevier Ltd. All rights reserved.

Using Fourier transform infrared grazing incidence reflectivity to study local vibrational modes in GaN

Both Fourier transform infrared (FTIR) grazing incidence reflectivity and FTIR transmission methods have been used to study GaN films grown on alpha-Al2O3 (0001) substrates by atmospheric pressure metal-organic chemical vapor deposition and low pressure metal-organic chemical vapor deposition. The results show that in the frequency range from 400 to 3500 cm(-1) the signal-to-noise ratio of the FTIR grazing incidence measurement is far higher than that of the FTIR transmission measurement. Some new vibrational structures appearing in the former measurement have been discussed. The features around 1460 and 1300 cm(-1) are tentatively assigned to scissoring and wagging local vibrational modes of CH2 in GaN, respectively. (C) 1999 American Institute of Physics. [S0021-8979(99)06509-3].

Raman scattering study on vibrational modes in Ga1-xMnxN prepared by Mn-ion implantation

Raman scattering measurements have been carried out on ferromagnetic semiconductor Ga1-xMnxN prepared by Mn-ion implantation and post annealing. The Raman results obtained from the annealed and un-annealed Ga1-xMnxN demonstrate that crystalline quality has been improved in Ga1-xMnxN after annealing. Some new vibrational modes in addition to GaN-like modes are found in the Raman spectra measured from the Ga1-xMnxN where the GaN-like modes are found to be shifted in the higher frequency side than those measured from the bulk GaN. A new vibrational mode observed is assigned to MnN-like mode. Other new phonon modes observed are assigned to disorder-activated modes and Mn-related vibrational modes caused by Mn-ion implantation and post-annealing. (c) 2006 Elsevier Ltd. All rights reserved.

Raman scattering study of vibrational modes and hole concentration in GaxMn1-xSb

The Raman scattering study of vibrational modes and hole concentration in a ferromagnetic semiconductor Ga1-xMnxSb grown by Mn ion implantation, deposition and post-annealing has been presented. The experiments are performed both in implanted and unimplanted regions before and after etching the samples. The Raman spectra measured from the unimplanted region show only GaSb-like phonon modes. On the other hand, the spectra measured from the implanted region show additional phonon modes approximately at 115, 152, 269, 437 and 659 cm(-1). The experimental results demonstrate that the extra modes are associated with surface defects, crystal disorder and blackish layer that is formed due to Mn ion implantation, deposition and annealing processes. Furthermore, we have determined the hole concentration as a function of laser probing position by modeling the Raman spectra using coupled mode theory. The contributions of GaSb-like phonon modes and coupled LO-phonon plasmon mode are taken into consideration in the model. The hole-concentration-dependent CLOPM is resolved in the spectra measured from the implanted and nearby implanted regions. The hole concentrations determined by Raman scattering are found to be in good agreement with those measured by the electrochemical capacitance-voltage technique.

AN ANALYSIS OF CHARGE STATES FOR LOCAL VIBRATIONAL-MODES BY OXYGEN DEFECTS IN SEMI-INSULATING GAAS

The high-resolution spectral measurements for new local vibrational modes near 714 cm-1 due to the oxygen defect in semi-insulating GaAs are analyzed on the basis of a model calculation by self-consistent bond orbital approach. Two charge states of oxygen atom with 1 and 2 extra electrons are assigned to be responsible for these local modes. The observed frequencies are explained by the properties of Ga-O-1 and Ga-O-2 bonds and the calculated cohesive energy indicates that the O-2 state is stable. The results are in good agreement with the kinetic analysis.

RELATION BETWEEN THE METASTABILITY OF EL2 AND THE PHOTOSENSITIVITY OF LOCAL VIBRATIONAL-MODES IN SEMIINSULATING GAAS

Recent infrared spectroscpic observations of local vibrational mode absorptions have revealed a number of photosensitive centers in semi-insulating GaAs. They include (OVAs) center which has three modes at 730 cm(-1) (A), 715 cm(-1) (B), and 714 cm(-1) (C), respectively, a suggested NH center related to a line at 983 cm(-1) (X(1)), and centers related to hydrogen, such as (H-O) or (H-N) bonds, corresponding to a group of peaks in the region of 2900-3500 cm(-1). The photosensitivity of various local vibration centers was observed to have similar time dependence under near-infrared illumination and was suggested to be due to their charge-state interconversion. Mainly described in this work is the effect of the 1.25-eV illumination. It is confirmed that this photoinduced kinetic process results from both electron capture and hole capture, which are closely related to the photoionization behavior and metastability of the EL2 center.

Resonant excitation of Mn local vibrational modes in the higher order Raman spectra of nanocrystalline Ga(1-x)Mn(x)N films

The effect of manganese on the vibrational properties of Ga(1-x)Mn(x)N (0 <= x <= 0.18) films has been investigated by Raman scattering using 488.0 and 632.8 nm photon excitations. The first-order transverse and longitudinal optical GaN vibrational bands were observed in the whole composition range using both excitations, while the corresponding overtones, as well as a prominent peak located in 1238 cm(-1) (153.5 meV) were only observed in the Mn-containing films under 488.0 nm excitation. We propose that the peak observed at 1238 cm(-1) is due to resonant Mn local vibrational modes, the excitation process being related to electronic transitions involving the Mn acceptor band.

Study of the Influence of Localized Vibrational Modes in Charge Transport Properties at Nanoscale Systems.

In molecular and atomic devices the interaction between electrons and ionic vibrations has an important role in electronic transport. The electron-phonon coupling can cause the loss of the electron's phase coherence, the opening of new conductance channels and the suppression of purely elastic ones. From the technological viewpoint phonons might restrict the efficiency of electronic devices by energy dissipation, causing heating, power loss and instability. The state of the art in electron transport calculations consists in combining ab initio calculations via Density Functional Theory (DFT) with Non-Equilibrium Green's Function formalism (NEGF). In order to include electron-phonon interactions, one needs in principle to include a self-energy scattering term in the open system Hamiltonian which takes into account the effect of the phonons over the electrons and vice versa. Nevertheless this term could be obtained approximately by perturbative methods. In the First Born Approximation one considers only the first order terms of the electronic Green's function expansion. In the Self-Consistent Born Approximation, the interaction self-energy is calculated with the perturbed electronic Green's function in a self-consistent way. In this work we describe how to incorporate the electron-phonon interaction to the SMEAGOL program (Spin and Molecular Electronics in Atomically Generated Orbital Landscapes), an ab initio code for electronic transport based on the combination of DFT + NEGF. This provides a tool for calculating the transport properties of materials' specific system, particularly in molecular electronics. Preliminary results will be presented, showing the effects produced by considering the electron-phonon interaction in nanoscale devices.

Joint statistical analysis of multiple measurement setups for the estimation of vibrational modes

Computing the modal parameters of large structures in Operational Modal Analysis often requires to process data from multiple non simultaneously recorded setups of sensors. These setups share some sensors in common, the so-called reference sensors that are fixed for all the measurements, while the other sensors are moved from one setup to the next. One possibility is to process the setups separately what result in different modal parameter estimates for each setup. Then the reference sensors are used to merge or glue the different parts of the mode shapes to obtain global modes, while the natural frequencies and damping ratios are usually averaged. In this paper we present a state space model that can be used to process all setups at once so the global mode shapes are obtained automatically and subsequently only a value for the natural frequency and damping ratio of each mode is computed. We also present how this model can be estimated using maximum likelihood and the Expectation Maximization algorithm. We apply this technique to real data measured at a footbridge.