868 research outputs found
Mass enhancement in narrow band systems
A perturbative study of the Holstein Molecular Crystal Model which accounts
for lattice structure and dimensionality effects is presented. Antiadiabatic
conditions peculiar of narrow band materials and an intermediate to strong
electron-phonon coupling are assumed. The polaron effective mass depends
crucially in all dimensions on the intermolecular coupling strengths which also
affect the size of the lattice deformation associated with the small polaron
formation.Comment: Istituto Nazionale di Fisica della Materia - Dipartimento di
Matematica e Fisica, Istituto Nazionale di Fisica della Materia Universita'
di Camerino, 62032 Camerino, Ital
Entropic Penalties in Circular DNA Assembly
The thermodynamic properties of DNA circular molecules are investigated by a
new path integral computational method which treats in the real space the
fundamental forces stabilizing the molecule. The base pair and stacking
contributions to the classical action are evaluated separately by simulating a
broad ensemble of twisted conformations. We obtain, for two short sequences, a
free energy landscape with multiple wells corresponding to the most convenient
values of helical repeat. Our results point to a intrinsic flexibility of the
circular structures in which the base pair fluctuations move the system from
one well to the next thus causing the local unwinding of the helix. The latter
is more pronounced in the shorter sequence whose cyclization causes a higher
bending stress. The entropic reductions associated to the formation of the
ordered helicoidal structure are estimated.Comment: The Journal of Chemical Physics (2014) in pres
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 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
Mass Renormalization in the Su-Schrieffer-Heeger Model
This study of the one dimensional Su-Schrieffer-Heeger model in a weak
coupling perturbative regime points out the effective mass behavior as a
function of the adiabatic parameter , is the
zone boundary phonon energy and is the electron band hopping integral.
Computation of low order diagrams shows that two phonons scattering processes
become appreciable in the intermediate regime in which zone boundary phonons
energetically compete with band electrons. Consistently, in the intermediate
(and also moderately antiadiabatic) range the relevant mass renormalization
signals the onset of a polaronic crossover whereas the electrons are
essentially undressed in the fully adiabatic and antiadiabatic systems. The
effective mass is roughly twice as much the bare band value in the intermediate
regime while an abrupt increase (mainly related to the peculiar 1D dispersion
relations) is obtained at .Comment: To be published in Phys.Rev.B - 3 figure
Path Integral of the Two Dimensional Su-Schrieffer-Heeger Model
The equilibrium thermodynamics of the two dimensional Su-Schrieffer-Heeger
Model is derived by means of a path integral method which accounts for the
variable range of the electronic hopping processes. While the lattice degrees
of freedom are classical functions of time and are integrated out exactly, the
electron particle paths are treated quantum mechanically. The free energy of
the system and its temperature derivatives are computed by summing at any
over the ensemble of relevant particle paths which mainly contribute to the
total partition function. In the low regime, the {\it heat capacity over T}
ratio shows un upturn peculiar of a glassy like behavior. This feature is more
sizeable in the square lattice than in the linear chain as the overall hopping
potential contribution to the total action is larger in higher dimensionality.Comment: Phys.Rev.B vol.71 (2005
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The multi-country transmission of sovereign and banking risk: a spatial vector autoregressive approach
This paper develops a spatial vector autoregressive (SpVAR) model to investigate the transmission of sovereign, banking, and corporate default risks among eleven Eurozone countries for the January 2008–December 2013 period. The results show that a significant proportion of default risk variation is explained by foreign shocks. However, the cross-border sovereign–bank nexus is statistically significant, but economically moderate. Among the three sectors, shocks to the banking sector play the most critical role. On average, for the eleven countries, a foreign banking shock can explain 7%, 23%, and 18% of the forecast error variance of changes in sovereign, banking, and corporate credit default swap (CDS) spreads, respectively
Nitrile ligands activation in dinuclear aminocarbyne complexes
The diiron complexes [Fe(Cp)(CO){μ-η2:η2-C[N(Me)(R)]NC(C6H3R′)CCH(Tol)}Fe(Cp)(CO)] (R = Xyl, R′ = H, 3a; R = Xyl, R′ = Br, 3b; R = Xyl, R′ = OMe, 3c; R = Xyl, R′ = CO2Me, 3d; R = Xyl, R′ = CF3, 3e; R = Me, R′ = H, 3f; R = Me, R′ = CF3, 3g) are obtained in good yields from the reaction of [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(p-NCC6H4R′)(Cp)2]+ (R = Xyl, R′ = H, 2a; R = Xyl, R′ = Br, 2b; R = Xyl, R′ = OMe, 2c; R = Xyl, R′ = CO2Me, 2d; R = Xyl, R′ = CF3, 2e; R = Me, R′ = H, 2f; R = Me, R′ = CF3, 2g) with TolCCLi. The formation of 3 involves addition of the acetylide at the coordinated nitrile and C–N coupling with the bridging aminocarbyne together with orthometallation of the p-substituted aromatic ring and breaking of the Fe–Fe bond. Complexes3a–e which contain the N(Me)(Xyl) group exist in solution as mixtures of the E-trans and Z-trans isomers, whereas the compounds 3f,g, which posses an exocyclic NMe2 group, exist only in the Z-cis form. The crystal structures of Z-trans-3b, E-trans-3c, Z-trans-3e and Z-cis-3g have been determined by X-ray diffraction experiments
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
Diiron-aminocarbyne complexes with amine or imine ligands: C-N coupling between imine and aminocarbyne ligands promoted by tolylacetilyde addition to [Fe2{m-CN(Me)R}(m-CO)(CO)(NH=CPh2)(Cp)2][SO3CF3]
A terminally coordinated CO ligand in the complexes [Fe2{m-CN(Me)R}(m-CO)(CO)2(Cp)2][SO3CF3] (R = Me, 1a; R = Xyl, 1b; Xyl = 2,6-Me2C6H3), is readily displaced by primary and secondary amines (L), in the presence of Me3NO, affording the complexes [Fe2{m-CN(Me)R}(m-CO)(CO)(L)(Cp)2][SO3CF3] (R = Me, L = NH2Et, 4a; R = Xyl, L = NH2Et, 4b; R = Me, L = NH2Pri, 5a; R = Xyl, L = NH2Pri, 5b; R = Xyl, L = NH2C6H11, 6; R = Xyl, L = NH2Ph, 7; R = Xyl, L = NH3, 8; R = Me, L = NHMe2, 9a; R = Xyl, L = NHMe2, 9b; R = Xyl, L= NH(CH2)5, 10). In the absence of Me3NO, NH2Et gives addition at the CO ligand of 1b, yielding [Fe2{CN(Me)(Xyl)}(m-CO)(CO)C(O)NHEt(Cp)2] (11). Carbonyl replacement is also observed in the reaction of 1a-b with pyridine and benzophenone imine, affording [Fe2{m-CN(Me)R}(m-CO)(CO)(L)(Cp)2][SO3CF3] (R= Me, L= Py, 12a; R = Xyl, L= Py, 12b; R= Me, L= HN=CPh2, 13a; R = Xyl, L= HN=CPh2, 13b). The imino complex 13b reacts with p-tolylacetylide leading to the formation of the m-vinylidene-diaminocarbene compound [Fe2-C=C(Tol)C(Ph)2N(H)CN(Me)(Xyl)(m-CO)(CO)(Cp2)] (15) which has been studied by X-ray diffraction
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