Electronic states in disordered topological insulators

We present a theoretical study of electronic states in topological insulators with impurities. Chiral edge states in 2d topological insulators and helical surface states in 3d topological insulators show a robust transport against nonmagnetic impurities. Such a nontrivial character inspired physicists to come up with applications such as spintronic devices [1], thermoelectric materials [2], photovoltaics [3], and quantum computation [4]. Not only has it provided new opportunities from a practical point of view, but its theoretical study has deepened the understanding of the topological nature of condensed matter systems. However, experimental realizations of topological insulators have been challenging. For example, a 2d topological insulator fabricated in a HeTe quantum well structure by Konig et al. [5] shows a longitudinal conductance which is not well quantized and varies with temperature. 3d topological insulators such as Bi₂Se₃ and Bi₂Te₃ exhibit not only a signature of surface states, but they also show a bulk conduction [6]. The series of experiments motivated us to study the effects of impurities and coexisting bulk Fermi surface in topological insulators. We first address a single impurity problem in a topological insulator using a semiclassical approach. Then we study the conductance behavior of a disordered topological-metal strip where bulk modes are associated with the transport of edge modes via impurity scattering. We verify that the conduction through a chiral edge channel retains its topological signature, and we discovered that the transmission can be succinctly expressed in a closed form as a ratio of determinants of the bulk Green's function and impurity potentials. We further study the transport of 1d systems which can be decomposed in terms of chiral modes. Lastly, the surface impurity effect on the local density of surface states over layers into the bulk is studied between weak and strong disorder strength limits.

Measurement of the neutron (^3He) spin structure function at low Q^2 : a connection between the Bjorken and Drell-Hearn-Gerasimov sum rules

The spin dependent cross sections, σT_1/2 and σT_3/2 , and asymmetries, A_∥ and A_⊥ for ³He have been measured at the Jefferson Lab's Hall A facility. The inclusive scattering process ³He(e,e)X was performed for initial beam energies ranging from 0.86 to 5.1 GeV, at a scattering angle of 15.5°. Data includes measurements from the quasielastic peak, resonance region, and the deep inelastic regime. An approximation for the extended Gerasimov-Drell-Hearn integral is presented at a 4-momentum transfer Q² of 0.2-1.0 GeV².

Also presented are results on the performance of the polarized ³He target. Polarization of ³He was achieved by the process of spin-exchange collisions with optically pumped rubidium vapor. The ³He polarization was monitored using the NMR technique of adiabatic fast passage (AFP). The average target polarization was approximately 35% and was determined to have a systematic uncertainty of roughly ±4% relative.

Band structure and transport properties of simple cubic tellurium-base alloys

The electrical transport properties and lattice spacings of simple cubic Te-Au, Te-Au-Fe, and Te-Au-Mn alloys, prepared by rapid quenching from the liquid state, hove been measured and correlated with a proposed bond structure. The variations of superconducting transition temperature, absolute thermoelectric power, and lattice spacing with Te concentration all showed related anomalies in the binary Te-Au alloys. The unusual behavior of these properties has been interpreted by using nearly free electron theory to predict the effect of the second Brillouin zone boundary on the area of the Fermi surface, and the electronic density of states. The behavior of the superconducting transition temperature and the lattice parameter as Fe and Mn ore added further supports the proposed interpretation as well as providing information on the existence of localized magnetic states in the ternary alloys. In addition, it was found that a very distinct bond structure effect on the transition temperatures of the Te-Au-Fe alloys could be identified.

First principles based multiparadigm modeling of electronic structures and dynamics

Electronic structures and dynamics are the key to linking the material composition and structure to functionality and performance.

An essential issue in developing semiconductor devices for photovoltaics is to design materials with optimal band gaps and relative positioning of band levels. Approximate DFT methods have been justified to predict band gaps from KS/GKS eigenvalues, but the accuracy is decisively dependent on the choice of XC functionals. We show here for CuInSe₂ and CuGaSe₂, the parent compounds of the promising CIGS solar cells, conventional LDA and GGA obtain gaps of 0.0-0.01 and 0.02-0.24 eV (versus experimental values of 1.04 and 1.67 eV), while the historically first global hybrid functional, B3PW91, is surprisingly the best, with band gaps of 1.07 and 1.58 eV. Furthermore, we show that for 27 related binary and ternary semiconductors, B3PW91 predicts gaps with a MAD of only 0.09 eV, which is substantially better than all modern hybrid functionals, including B3LYP (MAD of 0.19 eV) and screened hybrid functional HSE06 (MAD of 0.18 eV).

The laboratory performance of CIGS solar cells (> 20% efficiency) makes them promising candidate photovoltaic devices. However, there remains little understanding of how defects at the CIGS/CdS interface affect the band offsets and interfacial energies, and hence the performance of manufactured devices. To determine these relationships, we use the B3PW91 hybrid functional of DFT with the AEP method that we validate to provide very accurate descriptions of both band gaps and band offsets. This confirms the weak dependence of band offsets on surface orientation observed experimentally. We predict that the CBO of perfect CuInSe₂/CdS interface is large, 0.79 eV, which would dramatically degrade performance. Moreover we show that band gap widening induced by Ga adjusts only the VBO, and we find that Cd impurities do not significantly affect the CBO. Thus we show that Cu vacancies at the interface play the key role in enabling the tunability of CBO. We predict that Na further improves the CBO through electrostatically elevating the valence levels to decrease the CBO, explaining the observed essential role of Na for high performance. Moreover we find that K leads to a dramatic decrease in the CBO to 0.05 eV, much better than Na. We suggest that the efficiency of CIGS devices might be improved substantially by tuning the ratio of Na to K, with the improved phase stability of Na balancing phase instability from K. All these defects reduce interfacial stability slightly, but not significantly.

A number of exotic structures have been formed through high pressure chemistry, but applications have been hindered by difficulties in recovering the high pressure phase to ambient conditions (i.e., one atmosphere and room temperature). Here we use dispersion-corrected DFT (PBE-ulg flavor) to predict that above 60 GPa the most stable form of N₂O (the laughing gas in its molecular form) is a 1D polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03-0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions both polymers relax below 14 GPa to the same stable non-planar trans-polymer, accompanied by possible electronic structure transitions. The predicted phonon spectrum and dissociation kinetics validate the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a new type of conducting polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions.

Modeling non-adiabatic electron dynamics has been a long-standing challenge for computational chemistry and materials science, and the eFF method presents a cost-efficient alternative. However, due to the deficiency of FSG representation, eFF is limited to low-Z elements with electrons of predominant s-character. To overcome this, we introduce a formal set of ECP extensions that enable accurate description of p-block elements. The extensions consist of a model representing the core electrons with the nucleus as a single pseudo particle represented by FSG, interacting with valence electrons through ECPs. We demonstrate and validate the ECP extensions for complex bonding structures, geometries, and energetics of systems with p-block character (C, O, Al, Si) and apply them to study materials under extreme mechanical loading conditions.

Despite its success, the eFF framework has some limitations, originated from both the design of Pauli potentials and the FSG representation. To overcome these, we develop a new framework of two-level hierarchy that is a more rigorous and accurate successor to the eFF method. The fundamental level, GHA-QM, is based on a new set of Pauli potentials that renders exact QM level of accuracy for any FSG represented electron systems. To achieve this, we start with using exactly derived energy expressions for the same spin electron pair, and fitting a simple functional form, inspired by DFT, against open singlet electron pair curves (H₂ systems). Symmetric and asymmetric scaling factors are then introduced at this level to recover the QM total energies of multiple electron pair systems from the sum of local interactions. To complement the imperfect FSG representation, the AMPERE extension is implemented, and aims at embedding the interactions associated with both the cusp condition and explicit nodal structures. The whole GHA-QM+AMPERE framework is tested on H element, and the preliminary results are promising.

Band Engineering in Thermoelectric Materials Using Optical, Electronic, and Ab-Initio Computed Properties

Thermoelectric materials have demanded a significant amount of attention for their ability to convert waste heat directly to electricity with no moving parts. A resurgence in thermoelectrics research has led to significant enhancements in the thermoelectric figure of merit, zT, even for materials that were already well studied. This thesis approaches thermoelectric zT optimization by developing a detailed understanding of the electronic structure using a combination of electronic/thermoelectric properties, optical properties, and ab-initio computed electronic band structures. This is accomplished by applying these techniques to three important classes of thermoelectric materials: IV-VI materials (the lead chalcogenides), Half-Heusler’s (XNiSn where X=Zr, Ti, Hf), and CoSb₃ skutterudites.

In the IV-VI materials (PbTe, PbSe, PbS) I present a shifting temperature-dependent optical absorption edge which correlates well to the computed ab-initio molecular dynamics result. Contrary to prior literature that suggests convergence of the primary and secondary bands at 400 K, I suggest a higher convergence temperature of 700, 900, and 1000 K for PbTe, PbSe, and PbS, respectively. This finding can help guide electronic properties modelling by providing a concrete value for the band gap and valence band offset as a function of temperature.

Another important thermoelectric material, ZrNiSn (half-Heusler), is analyzed for both its optical and electronic properties; transport properties indicate a largely different band gap depending on whether the material is doped n-type or p-type. By measuring and reporting the optical band gap value of 0.13 eV, I resolve the discrepancy in the gap calculated from electronic properties (maximum Seebeck and resistivity) by correlating these estimates to the electron-to-hole weighted mobility ratio, A, in narrow gap materials (A is found to be approximately 5.0 in ZrNiSn).

I also show that CoSb₃ contains multiple conduction bands that contribute to the thermoelectric properties. These bands are also observed to shift towards each other with temperature, eventually reaching effective convergence for T>500 K. This implies that the electronic structure in CoSb₃ is critically important (and possibly engineerable) with regards to its high thermoelectric figure of merit.

Investigations of DNA-mediated protein oxidation

DNA charge transport (CT) involves the efficient transfer of electrons or electron holes through the DNA π-stack over long molecular distances of at least 100 base-pairs. Despite this shallow distance dependence, DNA CT is sensitive to mismatches or lesions that disrupt π-stacking and is critically dependent on proper electronic coupling of the donor and acceptor moieties into the base stack. Favorable DNA CT is very rapid, occurring on the picosecond timescale. Because of this speed, electron holes equilibrate along the DNA π-stack, forming a characteristic pattern of DNA damage at low oxidation potential guanine multiplets. Furthermore, DNA CT may be used in a biological context. DNA processing enzymes with 4Fe4S clusters can perform DNA-mediated electron transfer (ET) self-exchange reactions with other 4Fe4S cluster proteins, even if the proteins are quite dissimilar, as long as the DNA-bound [4Fe4S]^3+/2+ redox potentials are conserved. This mechanism would allow low copy number DNA repair proteins to find their lesions efficiently within the cell. DNA CT may also be used biologically for the long-range, selective activation of redox-active transcription factors. Within this work, we pursue other proteins that may utilize DNA CT within the cell and further elucidate aspects of the DNA-mediated ET self-exchange reaction of 4Fe4S cluster proteins.

Dps proteins, bacterial mini-ferritins that protect DNA from oxidative stress, are implicated in the survival and virulence of pathogenic bacteria. One aspect of their protection involves ferroxidase activity, whereby ferrous iron is bound and oxidized selectively by hydrogen peroxide, thereby preventing formation of damaging hydroxyl radicals via Fenton chemistry. Understanding the specific mechanism by which Dps proteins protect the bacterial genome could inform the development of new antibiotics. We investigate whether DNA-binding E. coli Dps can utilize DNA CT to protect the genome from a distance. An intercalating ruthenium photooxidant was employed to generate oxidative DNA damage via the flash-quench technique, which localizes to a low potential guanine triplet. We find that Dps loaded with ferrous iron, in contrast to Apo-Dps and ferric iron-loaded Dps which lack available reducing equivalents, significantly attenuates the yield of oxidative DNA damage at the guanine triplet. These data demonstrate that ferrous iron-loaded Dps is selectively oxidized to fill guanine radical holes, thereby restoring the integrity of the DNA. Luminescence studies indicate no direct interaction between the ruthenium photooxidant and Dps, supporting the DNA-mediated oxidation of ferrous iron-loaded Dps. Thus DNA CT may be a mechanism by which Dps efficiently protects the genome of pathogenic bacteria from a distance.

Further work focused on spectroscopic characterization of the DNA-mediated oxidation of ferrous iron-loaded Dps. X-band EPR was used to monitor the oxidation of DNA-bound Dps after DNA photooxidation via the flash-quench technique. Upon irradiation with poly(dGdC)₂, a signal arises with g = 4.3, consistent with the formation of mononuclear high-spin Fe(III) sites of low symmetry, the expected oxidation product of Dps with one iron bound at each ferroxidase site. When poly(dGdC)₂ is substituted with poly(dAdT)₂, the yield of Dps oxidation is decreased significantly, indicating that guanine radicals facilitate Dps oxidation. The more favorable oxidation of Dps by guanine radicals supports the feasibility of a long-distance protection mechanism via DNA CT where Dps is oxidized to fill guanine radical holes in the bacterial genome produced by reactive oxygen species.

We have also explored possible electron transfer intermediates in the DNA-mediated oxidation of ferrous iron-loaded Dps. Dps proteins contain a conserved tryptophan residue in close proximity to the ferroxidase site (W52 in E. coli Dps). In comparison to WT Dps, in EPR studies of the oxidation of ferrous iron-loaded Dps following DNA photooxidation, W52Y and W52A mutants were deficient in forming the characteristic EPR signal at g = 4.3, with a larger deficiency for W52A compared to W52Y. In addition to EPR, we also probed the role of W52 Dps in cells using a hydrogen peroxide survival assay. Bacteria containing W52Y Dps survived the hydrogen peroxide challenge more similarly to those containing WT Dps, whereas cells with W52A Dps died off as quickly as cells without Dps. Overall, these results suggest the possibility of W52 as a CT hopping intermediate.

DNA-modified electrodes have become an essential tool for the study of the redox chemistry of DNA processing enzymes with 4Fe4S clusters. In many cases, it is necessary to investigate different complex samples and substrates in parallel in order to elucidate this chemistry. Therefore, we optimized and characterized a multiplexed electrochemical platform with the 4Fe4S cluster base excision repair glycosylase Endonuclease III (EndoIII). Closely packed DNA films, where the protein has limited surface accessibility, produce EndoIII electrochemical signals sensitive to an intervening mismatch, indicating a DNA-mediated process. Multiplexed analysis allowed more robust characterization of the CT-deficient Y82A EndoIII mutant, as well as comparison of a new family of mutations altering the electrostatics surrounding the 4Fe4S cluster in an effort to shift the reduction potential of the cluster. While little change in the DNA-bound midpoint potential was found for this family of mutants, likely indicating the dominant effect of DNA-binding on establishing the protein redox potential, significant variations in the efficiency of DNA-mediated electron transfer were apparent. On the basis of the stability of these proteins, examined by circular dichroism, we proposed that the electron transfer pathway in EndoIII can be perturbed not only by the removal of aromatic residues but also through changes in solvation near the cluster.

While the 4Fe4S cluster of EndoIII is relatively insensitive to oxidation and reduction in solution, we have found that upon DNA binding, the reduction potential of the [4Fe4S]^3+/2+ couple shifts negatively by approximately 200 mV, bringing this couple into a physiologically relevant range. Demonstrated using electrochemistry experiments in the presence and absence of DNA, these studies do not provide direct molecular evidence for the species being observed. Sulfur K-edge X-ray absorbance spectroscopy (XAS) can be used to probe directly the covalency of iron-sulfur clusters, which is correlated to their reduction potential. We have shown that the Fe-S covalency of the 4Fe4S cluster of EndoIII increases upon DNA binding, stabilizing the oxidized [4Fe4S]³⁺ cluster, consistent with a negative shift in reduction potential. The 7% increase in Fe-S covalency corresponds to an approximately 150 mV shift, remarkably similar to DNA electrochemistry results. Therefore we have obtained direct molecular evidence for the shift in 4Fe4S reduction potential of EndoIII upon DNA binding, supporting the feasibility of our model whereby these proteins can utilize DNA CT to cooperate in order to efficiently find DNA lesions inside cells.

In conclusion, in this work we have explored the biological applications of DNA CT. We discovered that the DNA-binding bacterial ferritin Dps can protect the bacterial genome from a distance via DNA CT, perhaps contributing to pathogen survival and virulence. Furthermore, we optimized a multiplexed electrochemical platform for the study of the redox chemistry of DNA-bound 4Fe4S cluster proteins. Finally, we have used sulfur K-edge XAS to obtain direct molecular evidence for the negative shift in 4Fe4S cluster reduction potential of EndoIII upon DNA binding. These studies contribute to the understanding of DNA-mediated protein oxidation within cells.

I. Electron spin relaxation studies of manganese(II) complexes in acetonitrile. II. Nuclear spin relaxation studies of bromine in tetrabromomanganese(II) in acetonitrile

Magnetic resonance techniques have given us a powerful means for investigating dynamical processes in gases, liquids and solids. Dynamical effects manifest themselves in both resonance line shifts and linewidths, and, accordingly, require detailed analyses to extract desired information. The success of a magnetic resonance experiment depends critically on relaxation mechanisms to maintain thermal equilibrium between spin states. Consequently, there must be an interaction between the excited spin states and their immediate molecular environment which promote changes in spin orientation while excess magnetic energy is coupled into other degrees of freedom by non-radiative processes. This is well known as spin-lattice relaxation. Certain dynamical processes cause fluctuations in the spin state energy levels leading to spin-spin relaxation and, here again, the environment at the molecular level plays a significant role in the magnitude of interaction. Relatively few electron spin relaxation studies of solutions have been conducted and the present work is addressed toward the extension of our knowledge in this area and the retrieval of dynamical information from line shape analyses on a time scale comparable to diffusion controlled phenomena.

Specifically, the electron spin relaxation of three Mn⁺²3d⁵ complexes, Mn(CH₃CN)₆⁺², MnCl₄^-2 in acetonitrile has been studied in considerable detail. The effective spin Hamiltonian constants were carefully evaluated under a wide range of experimental conditions. Resonance widths of these Mn⁺² complexes were studied in the presence of various excess ligand ions and as a function of concentration, viscosity, temperature and frequency (X-band, ~9.5 Ԍ Hz and K-band, ~35 Ԍ Hz).

A number of interesting conclusions were drawn from these studies. For the Et₄NCl-₄^-2 system several relaxation mechanisms leading to resonance broadening were observed. One source appears to arise through spin-orbit interactions caused by modulation of the ligand field resulting from transient distortions of the complex imparted by solvent fluctuations in the immediate surroundings of the paramagnetic ion. An additional spin relaxation was assigned to the formation of ion pairs [Et₄N⁺…MnCl₄^-2] and it was possible to estimate the dissociation constant for this specie in acetonitrile.

The Bu₄NBr-MnBr₄^-2 study was considerably more interesting. As in the former case, solvent fluctuations and ion-pairing of the paramagnetic complex [Bu₄N⁺…MnBr₄^-2] provide significant relaxation for the electronic spin system. Most interesting, without doubt, is the onset of a new relaxation mechanism leading to resonance broadening which is best interpreted as chemical exchange. Thus, assuming that resonance widths were simply governed by electron spin state lifetimes, we were able to extract dynamical information from an interaction in which the initial and final states are the same

MnBr₄^-2 + Br^- = MnBr₄^-2 + Br^-.

The bimolecular rate constants were obtained at six different temperatures and their magnitudes suggested that the exchange is probably diffusion controlled with essentially a zero energy of activation. The most important source of spin relaxation in this system stems directly from dipolar interactions between the manganese 3d⁵ electrons. Moreover, the dipolar broadening is strongly frequency dependent indicating a deviation between the transverse and longitudinal relaxation times. We are led to the conclusion that the 3d⁵ spin states of ion-paired MnBr₄^-2 are significantly correlated so that dynamical processes are also entering the picture. It was possible to estimate the correlation time, ^Td, characterizing this dynamical process.

In Part II we study nuclear magnetic relaxation of bromine ions in the MnBr4-2-Bu4NBr-acetonitrile system. Essentially we monitor the 79Br and 81Br linewidths in response to the [MnBr4-2]/[Br-] ratio with the express purpose of supporting our contention that exchange is occurring between "free" bromine ions in the solvent and bromine in the first coordination sphere of the paramagnetic anion. The complexity of the system elicited a two-part study: (1) the linewidth behavior of Bu4NBr in anhydrous CH3CN in the absence of MnBr4-2 and (2) in the presence of MnBr4-2. It was concluded in study (1) that dynamical association, Bu4NBr k1= Bu4N+ + Br-, was modulating field-gradient interactions at frequencies high enough to provide an estimation of the unimolecular rate constant, k1. A comparison of the two isotopic bromine linewidth-mole fraction results led to the conclusion that quadrupole interactions provided the dominant relaxation mechanism. In study (2) the "residual" bromine linewidths for both 79Br and 81Br are clearly controlled by quadrupole interactions which appear to be modulated by very rapid dynamical processes other than molecular reorientation. We conclude that the "residual" linewidth has its origin in chemical exchange and that bromine nuclei exchange rapidly between a "free" solvated ion and the paramagnetic complex, MnBr4-2.

Electronic structure in five-coordinate complexes of nickel(II) with heavy-donor ligands

I.

Various studies designed to elucidate the electronic structure of the arsenic donor ligand, o-phenylenebisdimethylarsine (diarsine), have been carried out. The electronic spectrum of diarsine has been measured at 300 and 77˚K. Electronic spectra of the molecular complexes of various substituted organoarsines and phosphines with tetracyanoethylene have been measured and used to estimate the relative ionization potentials of these molecules.

Uv photolysis of arsines in frozen solution (96˚K) has yielded thermally labile, paramagnetic products. These include the molecular cations of the photolyzed compounds. The species (diars)⁺ exhibits hyper-fine splitting due to two equivalent ⁷⁵As(I=3/2) nuclei. Resonances due to secondary products are reported and assignments discussed.

Evidence is presented for the involvement of d-orbitals in the bonding of arsines. In (diars)⁺ there is mixing of arsenic “lone-pair” orbitals with benzene ring π-orbitals.

II.

Detailed electronic spectral measurements at 300 and 77˚K have been carried out on five-coordinate complexes of low-spin nickel(II), including complexes of both trigonal bipyramidal (TBP) and square pyramidal (SPY) geometry. TBP complexes are of the form NiLX⁺ (X=halide or cyanide,

L = Qƭ(CH₂)₃As(CH₃)₂]₃ or

P [hexagon - Q'CH₃] , Q = P, As,

Q’=S, Se).

The electronic spectra of these compounds exhibit a novel feature at low temperature. The first ligand field band, which is asymmetric in the room temperature solution spectrum, is considerably more symmetrical at 77˚K. This effect is interpreted in terms of changes in the structure of the complex.

The SPY complexes are of the form Ni(diars)₂X^z (X=CL, Br, CNS, CN, thiourea, NO₂, As). On the basis of the spectral results, the d-level ordering is concluded to be xy ˂ xz, yz ˂ z² ˂˂ x² - y². Central to this interpretation is identification of the symmetry-allowed ¹A₁ → ¹E (xz, yz → x² - y²) transition. This assignment was facilitated by the low temperature measurements.

An assignment of the charge-transfer spectra of the five-coordinate complexes is reported, and electronic spectral criteria for distinguishing the two limiting geometries are discussed.

I. Electronic processes in α-sulfur. II. Polaron motion in a D.C. electric field

Part I: The mobilities of photo-generated electrons and holes in orthorhombic sulfur are determined by drift mobility techniques. At room temperature electron mobilities between 0.4 cm²/V-sec and 4.8 cm²/V-sec and hole mobilities of about 5.0 cm²/V-sec are reported. The temperature dependence of the electron mobility is attributed to a level of traps whose effective depth is about 0.12 eV. This value is further supported by both the voltage dependence of the space-charge-limited, D.C. photocurrents and the photocurrent versus photon energy measurements.

As the field is increased from 10 kV/cm to 30 kV/cm a second mechanism for electron transport becomes appreciable and eventually dominates. Evidence that this is due to impurity band conduction at an appreciably lower mobility (4.10^-4 cm²/V-sec) is presented. No low mobility hole current could be detected. When fields exceeding 30 kV/cm for electron transport and 35 kV/cm for hole transport are applied, avalanche phenomena are observed. The results obtained are consistent with recent energy gap studies in sulfur.

The theory of the transport of photo-generated carriers is modified to include the case of appreciable thermos-regeneration from the traps in one transit time.

Part II: An explicit formula for the electric field E necessary to accelerate an electron to a steady-state velocity v in a polarizable crystal at arbitrary temperature is determined via two methods utilizing Feynman Path Integrals. No approximation is made regarding the magnitude of the velocity or the strength of the field. However, the actual electron-lattice Coulombic interaction is approximated by a distribution of harmonic oscillator potentials. One may be able to find the “best possible” distribution of oscillators using a variational principle, but we have not been able to find the expected criterion. However, our result is relatively insensitive to the actual distribution of oscillators used, and our E-v relationship exhibits the physical behavior expected for the polaron. Threshold fields for ejecting the electron for the polaron state are calculated for several substances using numerical results for a simple oscillator distribution.

Spin-helical Dirac states in graphene induced by polar-substrate surfaces with giant spin-orbit interaction: a new platform for spintronics

Spintronics, or spin electronics, is aimed at efficient control and manipulation of spin degrees of freedom in electron systems. To comply with demands of nowaday spintronics, the studies of electron systems hosting giant spin-orbit-split electron states have become one of the most important problems providing us with a basis for desirable spintronics devices. In construction of such devices, it is also tempting to involve graphene, which has attracted great attention because of its unique and remarkable electronic properties and was recognized as a viable replacement for silicon in electronics. In this case, a challenging goal is to lift spin degeneracy of graphene Dirac states. Here, we propose a novel pathway to achieve this goal by means of coupling of graphene and polar-substrate surface states with giant Rashba-type spin-splitting. We theoretically demonstrate it by constructing the graphene@BiTeCl system, which appears to possess spin-helical graphene Dirac states caused by the strong interaction of Dirac and Rashba electrons. We anticipate that our findings will stimulate rapid growth in theoretical and experimental investigations of graphene Dirac states with real spin-momentum locking, which can revolutionize the graphene spintronics and become a reliable base for prospective spintronics applications.

Preparation, characterization and gas sensing properties of high soluble metal (II) phthalocyanine thin films by spin-coating method

Three novel metal (II) phthalocyanine complexes were synthesized by cyclic tetramerisation reaction of a dicyano benzene component and different metal ions (Pd2+, Co2+, Zn2+). The structure of complexes was confirmed by elemental analysis, mass and IR spectrum. The excellent solubility of the complexes in benzene enabled us to obtain films by a spin-coating method. The films were characterized by IR, electronic spectral and AFM. The gas sensing properties to NO2 of the metal (II) phthalocyanine complex films were studied. In addition, the effects of different metal ions and the gas sensing temperature on the sensing properties were studied. (C) 2005 Elsevier B.V. All rights reserved.

Electronic properties of graphene grain boundaries

Grain boundaries and defect lines in graphene are intensively studied for their novel electronic and magnetic properties. However, there is not a complete comprehension of the appearance of localized states along these defects. Graphene grain boundaries are herein seen as the outcome of matching two semi-infinite graphene sheets with different edges. We classify the energy spectra of grain boundaries into three different types, directly related to the combination of the four basic classes of spectra of graphene edges. From the specific geometry of the grains, we are able to obtain the band structure and the number of localized states close to the Fermi energy. This provides a new understanding of states localized at grain boundaries, showing that they are derived from the edge states of graphene. Such knowledge is crucial for the ultimate tailoring of electronic and optoelectronic applications.

Temperature characteristics of optical parameters of phthalocyanine LB films and spin-coated films

The LB films and spin-coated films of tetra-neopentoxy phthalocyanine zinc (TNPPcZn) were prepared and annealed at different temperatures. Their refractive index (n) and extinction coefficient (k) were measured by p-polarized reflectance. The similar value of n and k, as well as similar changing tendency of it and k at varied annealing temperatures, was found between LB films and spin-coated films. In addition, the absorption curves of TNPPcZn LB films and spin-coated films in visible range at different annealing temperature were investigated. The results indicate that the changing tendency of the extinction coefficient of two kinds of TNPPcZn films obtained from two methods mentioned above were coincident. When the annealing temperature increased to 150 degrees C, the monomers of TNPPcZn films transformed to aggregates, n(f) and k(f) of the films increased. Further, n(f) and k(f) decreased as aggregates changed back to monomers again at the annealing temperature of 300 degrees C. The experimental results coincide well with the theoretical analysis. (C) 2004 Elsevier B.V. All rights reserved.

Defect and structural imperfection effects on the electronic properties of BiTeI surfaces

The surface electronic structure of the narrow-gap seminconductor BiTeI exhibits a large Rashba-splitting which strongly depends on the surface termination. Here we report on a detailed investigation of the surface morphology and electronic properties of cleaved BiTeI single crystals by scanning tunneling microscopy, photoelectron spectroscopy (ARPES, XPS), electron diffraction (SPA-LEED) and density functional theory calculations. Our measurements confirm a previously reported coexistence of Te- and I-terminated surface areas

A chemically inert Rashba split interface electronic structure of C-60, FeOEP and PTCDA on BiAg2/Ag(111) substrates

The fields of organic electronics and spintronics have the potential to revolutionize the electronics industry. Finding the right materials that can retain their electrical and spin properties when combined is a technological and fundamental challenge. We carry out the study of three archetypal organic molecules in intimate contact with the BiAg2 surface alloy. We show that the BiAg2 alloy is an especially suited substrate due to its inertness as support for molecular films, exhibiting an almost complete absence of substrate-molecular interactions. This is inferred from the persistence of a completely unaltered giant spin-orbit split surface state of the BiAg2 substrate, and from the absence of significant metallic screening of charged molecular levels in the organic layer. Spin-orbit split states in BiAg2 turn out to be far more robust to organic overlayers than previously thought.