arXiv subjects
Publications and source records attributed to Erio Tosatti.
We have investigated infinitely long, monostrand Pt nanowires theoretically, and found that they exhibit Hund's rule magnetism. We find a spin moment of 0.6 Bohr magnetons per atom, at the equilibrium bond length. Its magnetic moment increases with stretching. The origin of the wire magnetism is analyzed and its effect on the conductance through the wire is discussed.
The h_u hole spectral intensity for C60 -> C60+ molecular photoemission is calculated at finite temperature by a parameter-free Lanczos diagonalization of the electron-vibration Hamiltonian, including the full 8 H_g, 6 G_g, and 2 A_g mode couplings. The computed spectrum at 800 K is in striking agreement with gas-phase data. The energy separation of the first main shoulder from the main photoemission peak, 230 meV in C60, is shown to measure directly and rather generally the strength of the final-state Jahn-Teller coupling.
A recent Letter reports photoemission data for the free C60 molecule, showing an interesting three-peak structure, presented as evidence of dynamic Jahn-Teller (DJT) effect in the C60+ ion. Those data constitute, along with earlier spectra by the Uppsala group, the best available piece of experimental evidence about the spectrum of a hole in fullerene. DJT must indeed affect the fivefold-degenerate h_u hole molecular orbital, but we contend that the energy separation of these three peaks is far too large for the proposed tunneling interpretation to be correct.
We investigate the occurrence of Hund's rule magnetism in C60(n+-) molecular ions, by computing the ground-state spin for all charge states n from -3 to +5. The two competing interactions, electron-vibration (e-v, including Jahn Teller, favoring low spin) and electron-electron (e-e, including Hund-rule exchange, favoring high spin), are accounted for based on previously computed ab-initio coupling parameters. Treating the ion coordinates as classical, we first calculate and classify the static Jahn-Teller distorted states for all n, inclusive of both e-v and e-e effects. We then correct the adiabatic result by including the zero-point energy lowering associated with softening of vibrations at the adiabatic Jahn-Teller minima. Our overall result is that while, like in previous investigations, low-spin states prevail in negative ions, Hund's rule high spin dominates all positive C60(n+) ions. This suggests also that Hund-rule magnetism could arise in fullerene cation-based solid state compounds, particularly those involving C60(2+).
We have carried out fully relativistic full-potential, spin-polarized, all-electron density-functional calculations for straight, monatomic nanowires of the 5d transition and noble metals Os, Ir, Pt and Au. We find that, of these metal nanowires, Os and Pt have mean-field magnetic moments for values of the bond length at equilibrium. In the case of Au and Ir, the wires need to be slightly stretched in order to spin polarize. An analysis of the band structures of the wires indicate that the superparamagnetic state that our calculations suggest will affect the conductance through the wires -- though not by a large amount -- at least in the absence of magnetic domain walls. It should thus lead to a characteristic temperature- and field dependent conductance, and may also cause a significant spin polarization of the transmitted current.
The complex band structure of an isolated polyethylene chain is calculated within Density Functional Theory (DFT). A plane wave basis and ultrasoft pseudopotentials are used. The results are compared with those obtained via a local basis set. We obtain a gap between the highest occupied molecular orbilar (HOMO) and the antibonding unoccupied molecular orbitals of 9.3 eV and a non-resonant tunneling $β$ parameter of 0.9 per monomer, in reasonable agreement with experiment and with results obtained via local basis. Polyethylene is a negative electron affinity material and the actual gap should be the energy of the HOMO with respect to the vacuum level (in DFT approximation only about 5.14 eV). The Bloch states at imaginary k are mainly free-electron-like parabolic bands which are missing in the local basis. We present also the complex bands of the bulk polyethylene in order to estimate the effects of the chain-chain interactions on the complex band structure. The relevance of these results for the tunnelling conduction of n-alkane chains is discussed.
We compute, based on density-functional electronic-structure calculations, the Coulomb couplings in the h_u highest occupied orbital of molecular C60. We obtain a multiplet-averaged Hubbard U ~ 3 eV, and four Hund-rule-like intra-molecular multiplet-splitting terms, each of the order of few hundreds of meVs. According to these couplings, all C60^n+ ions should possess a high-spin ground state if kept in their rigid, undistorted form. Even after molecular distortions are allowed, however, the Coulomb terms still appear to be somewhat stronger than the previously calculated Jahn-Teller couplings, the latter favoring low-spin states. Thus for example in C60^2+, unlike C60^2-, the balance between Hund rule and Jahn Teller yields, even if marginally, a high-spin ground state. That seems surprising in view of reports of superconductivity in field-doped C60^n+ systems.
Probing the lowest energy configuration of a complex system by quantum annealing was recently found to be more effective than its classical, thermal counterpart. Comparing classical and quantum Monte Carlo annealing protocols on the random two-dimensional Ising model we confirm the superiority of quantum annealing relative to classical annealing. We also propose a theory of quantum annealing, based on a cascade of Landau-Zener tunneling events. For both classical and quantum annealing, the residual energy after annealing is inversely proportional to a power of the logarithm of the annealing time, but the quantum case has a larger power which makes it faster
Within dynamical mean-field theory, we study the metal-insulator transition of a twofold orbitally degenerate Hubbard model as a function of a splitting Δof the degeneracy. The phase diagram in the U-Δplane exhibits two-band and one-band metals, as well as the Mott insulator. The correlated two-band metal is easily driven to the insulator state by a strikingly weak splitting Δ<< W of the order of the Kondo-peak width zW, where z << 1 is the metal quasiparticle weight. The possible relevance of this result to the insulator-metal transition in the orthorhombic expanded fulleride NH3 K3C60 is discussed.
Recent experiments have shown that C60 can be positively field-doped. In that state, fullerene exhibits a higher resistivity and a higher superconducting temperature than the corresponding negatively doped state. A strong intramolecular hole-phonon coupling, connected with the Jahn-Teller effect of the isolated positive ion, is expected to be important for both properties, but the actual coupling strengths are so far unknown. Based on density functional calculations, we determine the linear couplings of the two a_g, six g_g, and eight h_g vibrational modes to the H_u HOMO level of the C60 molecule. The couplings predict a D_5 distortion, and an H_u vibronic ground state for C60^+. They are also used to generate the dimensionless coupling constant which controls the superconductivity and the phonon contribution to the electrical resistivity in the crystalline phase. We find that is 1.4 times larger in positively-charged C60 than in the negatively-doped case. These results are discussed in the context of the available transport data and superconducting temperatures. The role of higher orbital degeneracy in superconductivity is also addressed.
A model for correlated electrons in a lattice with local additional spin--1 degrees of freedom inducing constrained hopping, is studied both in the low density limit and at quarter filling. We show that in both 1D and 2D two particles form a bound state even in presence of a repulsive U<U_c. A picture of a dilute Bose gas, leading to off-diagonal long range order (LRO) in 2D (quasi-LRO in 1D), is supported by quantitative calculations in 1D which allow for a determination of the phase diagram.
Recent lattice model calculations have suggested that a full-layered crystal surface may undergo, under canonical (particle-conserving) conditions, a preroughening-driven two-dimensional phase separation into two disordered flat (DOF) regions, of opposite order parameter. We have carried out extensive classical molecular dynamics (MD) simulations of the Lennard-Jones fcc(111) surface, to check whether these predictions are relevant or not for a realistic continuous system. Very long simulation times, a grid of temperatures from (2/3)Tm to Tm, and unusually large system sizes are employed to ensure full equilibrium and good statistics. By examining layer-by-layer occupancies, height fluctuations, sublattice order parameter and X-ray structure factors, we find a clear anomaly at ~0.83Tm. The anomaly is distinct from roughening (whose incipiency is also detected at ~0.94Tm), and is seen to be consistent with the preroughening plus phase separation scenario.
A new class of strongly infrared active structures is identified for phase III of compressed molecular H2 by constant-pressure ab initio molecular dynamics and density-functional perturbation calculations. These are planar quadrupolar structures obtained as a distortion of low-pressure quadrupolar phases, after they become unstable at about 150 GPa due to a zone-boundary soft phonon. The nature of the II-III transition and the origin of the IR activity are rationalized by means of simple electrostatics, as the onset of a stabilizing dipole-quadrupole interaction.
The theory of the preroughening transition of an unreconstructed surface, and the ensuing disordered flat (DOF) phase, is formulated in terms of interacting steps. Finite terraces play a crucial role in the formulation. We start by mapping the statistical mechanics of interacting (up and down) steps onto the quantum mechanics of two species of one-dimensional hard-core bosons. The effect of finite terraces translates into a number-non-conserving term in the boson Hamiltonian, which does not allow a description in terms of fermions, but leads to a two-chain spin problem. The Heisenberg spin-1 chain is recovered as a special limiting case. The global phase diagram is rich. We find the DOF phase is stabilized by short-range repulsions of like steps. On-site repulsion of up-down steps is essential in producing a DOF phase, whereas an off-site attraction between them is favorable but not required. Step-step correlation functions and terrace width distributions can be directly calculated with this method.
We discuss a hopping model of electrons between idealized molecular sites with local orbital degeneracy and dynamical Jahn-Teller effect, for crystal field environments of sufficiently high symmetry. For the Mott-insulating case (one electron per site and large Coulomb repulsions), in the simplest two-fold degenerate situation, we are led to consider a particular exchange hamiltonian, describing two isotropic spin-1/2 Heisenberg problems coupled by a quartic term on equivalent bonds. This twin-exchange hamiltonian applies to a physical regime in which the inter-orbital singlet is the lowest-energy intermediate state available for hopping. This regime is favored by a relatively strong electron-phonon coupling. Using variational arguments, a large-N limit, and exact diagonalization data, we find that the ground state, in the one dimensional case, is a solid valence bond state. The situation in the two dimensional case is less clear. Finally, the behavior of the system upon hole doping is studied in one dimension.
Motivated by the recent experimental evidence of commensurate surface charge density waves (CDW) in Pb/Ge(111) and Sn/Ge(111) sqrt{3}-adlayer structures, as well as by the insulating states found on K/Si(111):B and SiC(0001), we have investigated the role of electron-electron interactions, and also of electron-phonon coupling, on the narrow surface state band originating from the outer dangling bond orbitals of the surface. We model the sqrt{3} dangling bond lattice by an extended two-dimensional Hubbard model at half-filling on a triangular lattice. We include an on-site Hubbard repulsion U and a nearest-neighbor Coulomb interaction V, plus a long-ranged Coulomb tail. The electron-phonon interaction is treated in the deformation potential approximation. We have explored the phase diagram of this model including the possibility of commensurate 3x3 phases, using mainly the Hartree-Fock approximation. For U larger than the bandwidth we find a non-collinear antiferromagnetic SDW insulator, possibly corresponding to the situation on the SiC and K/Si surfaces. For U comparable or smaller, a rich phase diagram arises, with several phases involving combinations of charge and spin-density-waves (SDW), with or without a net magnetization. We find that insulating, or partly metallic 3x3 CDW phases can be stabilized by two different physical mechanisms. One is the inter-site repulsion V, that together with electron-phonon coupling can lower the energy of a charge modulation. The other is a novel magnetically-induced Fermi surface nesting, stabilizing a net cell magnetization of 1/3, plus a collinear SDW, plus an associated weak CDW. Comparison with available experimental evidence, and also with first-principle calculations is made.
A thin plate or slab, prepared so that opposite faces have different surface stresses, will bend as a result of the stress difference. We have developed a classical molecular dynamics (MD) formulation where (similar in spirit to constant-pressure MD) the curvature of the slab enters as an additional dynamical degree of freedom. The equations of motion of the atoms have been modified according to a variable metric, and an additional equation of motion for the curvature is introduced. We demonstrate the method to Au surfaces, both clean and covered with Pb adsorbates, using many-body glue potentials. Applications to stepped surfaces, deconstruction and other surface phenomena are under study.
We find the exact semiclassical (strong coupling) zero-point energy shifts applicable to the $e\otimes (n E)$ and $t\otimes (n H)$ dynamic Jahn-Teller problems, for an arbitrary number $n$ of discrete vibrational modes simultaneously coupled to one single electronic level. We also obtain an analytical formula for the frequency of the resulting normal modes, which has an attractive and apparently general Slater-Koster form. The limits of validity of this approach are assessed by comparison with O'Brien's previous effective-mode approach, and with accurate numerical diagonalizations. Numerical values obtained for $t\otimes (n H)$ with $n =8$ and coupling constants appropriate to C$_{60}^-$ are used for this purpose, and are discussed in the context of fullerene.