Polaron Crossover in Molecular Solids

An analytical variational method is applied to the molecular Holstein Hamiltonian in which the dispersive features of the dimension dependent phonon spectrum are taken into account by a force constant approach. The crossover between a large and a small size polaron is monitored, in one, two and three dimensions and for different values of the adiabatic parameter, through the behavior of the effective mass as a function of the electron-phonon coupling. By increasing the strength of the inter-molecular forces the crossover becomes smoother and occurs at higher {\it e-ph} couplings. These effects are more evident in three dimensions. We show that our Modified Lang-Firsov method starts to capture the occurence of a polaron self-trapping transition when the electron energies become of order of the phonon energies. The self-trapping event persists in the fully adiabatic regime. At the crossover we estimate polaron effective masses of order $\sim 5 - 40$ times the bare band mass according to dimensionality and value of the adiabatic parameter. Modified Lang-Firsov polaron masses are substantially reduced in two and three dimensions. There is no self-trapping in the antiadiabatic regime.Comment: To be published in J.Phys.:Condensed Matte

Non Local Electron-Phonon Correlations in a Dispersive Holstein Model

Due to the dispersion of optical phonons, long range electron-phonon correlations renormalize downwards the coupling strength in the Holstein model. We evaluate the size of this effect both in a linear chain and in a square lattice for a time averaged {\it e-ph} potential, where the time variable is introduced according to the Matsubara formalism. Mapping the Holstein Hamiltonian onto the time scale we derive the perturbing source current which appears to be non time retarded. This property permits to disentangle phonon and electron coordinates in the general path integral for an electron coupled to dispersive phonons. While the phonon paths can be integrated out analytically, the electron path integrations have to be done numerically. The equilibrium thermodynamic properties of the model are thus obtained as a function of the electron hopping value and of the phonon spectrum parameters. We derive the {\it e-ph} corrections to the phonon free energy and show that its temperature derivatives do not depend on the {\it e-ph} effective coupling hence, the Holstein phonon heat capacity is strictly harmonic. A significant upturn in the low temperature total heat capacity over $T$ ratio is attributed to the electron hopping which largely contributes to the action.Comment: Phys.Rev.B (2005

Thermodynamic properties of Holstein polarons and the effects of disorder

The ground state and finite temperature properties of polarons are studied considering a two-site and a four-site Holstein model by exact diagonalization of the Hamiltonian. The kinetic energy, Drude weight, correlation functions involving charge and lattice deformations, and the specific heat have been evaluated as a function of electron-phonon (e-ph) coupling strength and temperature. The effects of site diagonal disorder on the above properties have been investigated. The disorder is found to suppress the kinetic energy and the Drude weight, reduces the spatial extension of the polaron, and makes the large-to-small polaron crossover smoother. Increasing temperature also plays similar role. For strong coupling the kinetic energy arises mainly from the incoherent hopping processes owing to the motion of electrons within the polaron and is almost independent of the disorder strength. From the coherent and incoherent contributions to the kinetic energy, the temperature above which the incoherent part dominates is determined as a function of e-ph coupling strength.Comment: 17 pages. 17 figure

Path Integral Description of a Semiclassical Su-Schrieffer-Heeger Model

The electron motion along a chain is described by a continuum version of the Su-Schrieffer-Heeger Hamiltonian in which phonon fields and electronic coordinates are mapped onto the time scale. The path integral formalism allows us to derive the non local source action for the particle interacting with the oscillators bath. The method can be applied for any value of the {\it e-ph} coupling. The path integral dependence on the model parameters has been analysed by computing the partition function and some thermodynamical properties from $T= 1K$ up to room temperature. A peculiar upturn in the low temperature {\it heat capacity over temperature} ratio (pointing to a glassy like behavior) has been ascribed to the time dependent electronic hopping along the chain

Polaron self-trapping in a honeycomb net

Small polaron behavior in a two dimensional honeycomb net is studied by applying the strong coupling perturbative method to the Holstein molecular crystal model. We find that small optical polarons can be mobile also if the electrons are strongly coupled to the lattice. Before the polarons localize and become very heavy, there is infact a window of {\it e-ph} couplings in which the polarons are small and have masses of order $\simeq 5 - 50$ times the bare band mass according to the value of the adiabaticity parameter. The 2D honeycomb net favors the mobility of small optical polarons in comparison with the square lattice.Comment: 6 pages, 3 figures, to appear in J.Phys.:Condensed Matter {PACS: 63.10.+a, 63.20.Dj, 71.38.+i

Spatial inversion of gyrotropy parameter in conductivity tensor and charge transport peculiarities

Charge transfer is discussed for the case when gyrotropy parameter (Hall coefficient) varies along transport л-direction and inverses its sign. This situation takes place in contacts of the serially joined materials having electron and hole types of conductivity. Spatial inhomogeneity of conductivity and inversion of Hall coefficient sign are analyzed in terms of electric potential and current density distribution. It is shown that under inhomogeneous magnetic field the steady current skinning takes place in plate sample

Ti3SiC2-Cf composites by spark plasma sintering: Processing, microstructure and thermo-mechanical properties

MAX phases, and particularly Ti3SiC2, are interesting for high temperature applications. The addition of carbon fibers can be used to reduce the density and to modify the properties of the matrix. This work presents the densification and characterization of Ti3SiC2 based composites with short carbon fibers using a fast and simple fabrication approach: dry mixing and densification by Spark Plasma Sintering. Good densification level was obtained below 1400 °C even with a high amount of fibers. The reaction of the fibers with the matrix is limited thanks to the fast processing time and depends on the amount of fibers in the composite. Bending strength at room temperature, between 437 and 120 MPa, is in the range of conventional CMCs with short fibers and according to the resistance of the matrix and the presence of residual porosity. Thermo-mechanical properties of the composites up to 1500 °C are also presented.This work has received funding from the European Union’s Horizon2020 “Research and innovation programme” under grant agreement No 685594 (C3HARME

Particle Path Correlations in a Phonon Bath

The path integral formalism is applied to derive the full partition function of a generalized Su-Schrieffer-Heeger Hamiltonian describing a particle motion in a bath of oscillators. The electronic correlations are computed versus temperature for some choices of oscillators energies. We study the perturbing effect of a time averaged particle path on the phonon subsystem deriving the relevant temperature dependent cumulant corrections to the harmonic partition function and free energy. The method has been applied to compute the total heat capacity up to room temeperature: a low temperature upturn in the heat capacity over temperature ratio points to a glassy like behavior ascribable to a time dependent electronic hopping with variable range in the linear chain.Comment: To be published in J.Phys.:Condensed Matte

Path Integral of the Holstein Model with a ϕ4\phi^4 on site potential

We derive the path integral of the semiclassical, one dimensional anharmonic Holstein model assuming that the electron motion takes place in a bath of non linear oscillators with quartic on site hard (and soft) potentials. The interplay between {\it e-ph} coupling and anharmonic force constant is analysed both in the adiabatic and antiadiabatic regime. In the latter we find much larger anharmonic features on the thermodynamic properties of low energy oscillators. Soft on site potentials generate attractive centres at large amplitude oscillator paths and contribute to the anomalous shape of the {\it heat capacity over temperature} ratio in the intermediate to low $T$ range. This anharmonic lattice effect is superimposed to the purely electronic contribution associated to a temperature dependent hopping with variable range inducing local disorder in the system.Comment: To be published in Phys.Rev.

Polarons and slow quantum phonons

We describe the formation and properties of Holstein polarons in the entire parameter regime. Our presentation focuses on the polaron mass and radius, which we obtain with an improved numerical technique. It is based on the combination of variational exact diagonalization with an improved construction of phonon states, providing results even for the strong coupling adiabatic regime. In particular we can describe the formation of large and heavy adiabatic polarons. A comparison of the polaron mass for the one and three dimensional situation explains how the different properties in the static oscillator limit determine the behavior in the adiabatic regime. The transport properties of large and small polarons are characterized by the f-sum rule and the optical conductivity. Our calculations are approximation-free and have negligible numerical error. This allows us to give a conclusive and impartial description of polaron formation. We finally discuss the implications of our results for situations beyond the Holstein model.Comment: Final version, 10 pages, 10 figure