Quantum transport through single-molecule junctions with orbital degeneracies

We consider electronic transport through a single-molecule junction where the molecule has a degenerate spectrum. Unlike previous transport models, and theories a rate-equations description is no longer possible, and the quantum coherences between degenerate states have to be taken into account. We present the derivation and application of a master equation that describes the system in the weak-coupling limit and give an in-depth discussion of the parameter regimes and the new phenomena due to coherent on-site dynamics

Numerical adiabatic potentials of orthorhombic Jahn-Teller effects retrieved from ultrasound attenuation experiments. Application to the SrF2:Cr crystal

A methodology is worked out to retrieve the numerical values of all the main parameters of the six-dimensional adiabatic potential energy surface (APES) of a polyatomic system with a quadratic T-term Jahn-Teller effect (JTE) from ultrasound experiments. The method is based on a verified assumption that ultrasound attenuation and speed encounter anomalies when the direction of propa- gation and polarization of its wave of strain coincides with the characteristic directions of symmetry breaking in the JTE. For the SrF2:Cr crystal, employed as a basic example, we observed anomaly peaks in the temperature dependence of attenuation of ultrasound at frequencies of 50-160 MHz in the temperature interval of 40-60 K for the wave propagating along the [110] direction, for both the longitudinal and shear modes, the latter with two polarizations along the [001] and [110] axes, respectively. We show that these anomalies are due to the ultrasound relaxation by the system of non-interacting Cr2+ JT centers with orthorhombic local distortions. The interpretation of the ex- perimental findings is based on the T2g (eg +t2g) JTE problem including the linear and quadratic terms of vibronic interactions in the Hamiltonian and the same-symmetry modes reduced to one interaction mode. Combining the experimental results with a theoretical analysis we show that on the complicated six-dimensional APES of this system with three tetragonal, four trigonal, and six orthorhombic extrema points, the latter are global minima, while the former are saddle points, and we estimate numerically all the main parameters of this surface, including the linear and quadratic vibronic coupling constants, the primary force constants, the coordinates of all the extrema points and their energies, the energy barrier between the orthorhombic minima, and the tunneling splitting of the ground vibrational states.Comment: 8 pages, 3 figure

Giant isotope effect and spin state transition induced by oxygen isotope exchange in (Pr1−xSmx)0.7Ca0.3CoO3Pr_{1-x}Sm_x)_{0.7}Ca_{0.3}CoO_3

We systematically investigate effect of oxygen isotope in $(Pr_{1-x}Sm_x)_{0.7}Ca_{0.3}CoO_3$ which shows a crossover with x from ferromagnetic metal to the insulator with spin-state transition. A striking feature is that effect of oxygen isotope on the ferromagnetic transition is negligible in the metallic phase, while replacing $^{16}O$ with $^{18}O$ leads to a giant up-shift of the spin-state transition temperature ($T_s$) in the insulating phase, especially $T_s$ shifts from 36 to 54 K with isotope component $\alpha_S=-4.7$ for the sample with x=0.175. A metal-insulator transition is induced by oxygen isotope exchange in the sample x=0.172 being close to the insulating phase. The contrasting behaviors observed in the two phases can be well explained by occurrence of static Jahn-Teller distortions in the insulating phase, while absence of them in the metallic phase.Comment: 4 pages, 5 figure

The role of nitrogen-related defects in high-k dielectric oxides: Density-functional studies

Using ab initio density-functional total energy and molecular-dynamics simulations, we study the effects of various forms of nitrogen postdeposition anneal(PDA) on the electric properties of hafnia in the context of its application as a gate dielectric in field-effect transistors. We consider the atomic structure and energetics of nitrogen-containing defects which can be formed during PDA in various N-based ambients: N2, N2+, N, NH3, NO, and N2O. We analyze the role of such defects in fixed charge accumulation, electron trapping, and in the growth of the interface SiO2 layer. We find that nitrogen anneal of the oxides leads to an effective immobilization of native defects such as oxygen vacancies and interstitial oxygen ions, which may inhibit the growth of a silica layer. However, nitrogen in any form is unlikely to significantly reduce the fixed charge in the dielectric.Peer reviewe

Field-induced level crossings in spin clusters: Thermodynamics and magneto-elastic instability

Quantum spin clusters with dominant antiferromagnetic Heisenberg exchange interactions typically exhibit a sequence of field-induced level crossings in the ground state as function of magnetic field. For fields near a level crossing, the cluster can be approximated by a two-level Hamiltonian at low temperatures. Perturbations, such as magnetic anisotropy or spin-phonon coupling, sensitively affect the behavior at the level-crossing points. The general two-level Hamiltonian of the spin system is derived in first-order perturbation theory, and the thermodynamic functions magnetization, magnetic torque, and magnetic specific heat are calculated. Then a magneto-elastic coupling is introduced and the effective two-level Hamilitonian for the spin-lattice system derived in the adiabatic approximation of the phonons. At the level crossings the system becomes unconditionally unstable against lattice distortions due to the effects of magnetic anisotropy. The resultant magneto-elastic instabilities at the level crossings are discussed, as well as the magnetic behavior.Comment: 13 pages, 8 figures, REVTEX

Low-energy excitations of a linearly Jahn-Teller coupled orbital quintet

The low-energy spectra of the single-mode h x (G+H) linear Jahn-Teller model is studied by means of exact diagonalization. Both eigenenergies and photoemission spectral intensities are computed. These spectra are useful to understand the vibronic dynamics of icosahedral clusters with partly filled orbital quintet molecular shells, for example C60 positive ions.Comment: 14 pages revte

Dissociative electron attachment to the H2O molecule. II. Nuclear dynamics on coupled electronic surfaces within the local complex potential model

We report the results of a first-principles study of dissociative electron attachment to H2O. The cross sections are obtained from nuclear dynamics calculations carried out in full dimensionality within the local complex potential model by using the multi-configuration time-dependent Hartree method. The calculations employ our previously obtained global, complex-valued, potential-energy surfaces for the three (doublet B1, doublet A1, and doublet B2) electronic Feshbach resonances involved in this process. These three metastable states of H2O- undergo several degeneracies, and we incorporate both the Renner-Teller coupling between the B1 and A1 states as well as the conical intersection between the A1 and B2 states into our treatment. The nuclear dynamics are inherently multidimensional and involve branching between different final product arrangements as well as extensive excitation of the diatomic fragment. Our results successfully mirror the qualitative features of the major fragment channels observed, but are less successful in reproducing the available results for some of the minor channels. We comment on the applicability of the local complex potential model to such a complicated resonant system.Comment: Corrected version of Phys Rev A 75, 012711 (2007

Correlation between the nanoscale electrical and morphological properties of crystallized hafnium oxide-based metal oxide semiconductor structures

The relationship between electrical and structuralcharacteristics of polycrystalline HfO2films has been investigated by conductive atomic force microscopy under ultrahigh vacuum conditions. The results demonstrate that highly conductive and breakdown (BD) sites are concentrated mainly at the grain boundaries (GBs). Higher conductivity at the GBs is found to be related to their intrinsic electrical properties, while the positions of the electrical stress-induced BD sites correlate to the local thinning of the dielectric. The results indicate that variations in the local characteristics of the high-k film caused by its crystallization may have a strong impact on the electrical characteristics of high-k dielectric stacks

Role of Orbitals in the Physics of Correlated Electron Systems

Rich properties of systems with strongly correlated electrons, such as transition metal oxides, is largely connected with an interplay of different degrees of freedom in them: charge, spin, orbital ones, as well as crystal lattice. Specific and often very important role is played by orbital degrees of freedom. In this comment I will shortly summarize the main concepts and discuss some of the well-known manifestations of orbital degrees of freedom, but will mostly concentrate on a recent development in this field.Comment: To be published in "Comments on Solid State Physics", part of "Physica Scripta