arXiv subjects

Erik Vesselli

Publications and source records attributed to Erik Vesselli.

5 recordsLinked to original sources

arXiv2022

Growing borophene on metal substrates: a theoretical study of the role of oxygen on Al(111)

Charge transfer from a metal substrate stabilizes honeycomb borophene, whose electron deficit would otherwise spoil the hexagonal order of a $π$-bonded 2D atomic network. However, the coupling between the substrate and the boron overlayer may result in the formation of strong chemical bonds that would compromise the electronic properties of the overlayer. In this paper we present a theoretical study, based on state-of-the-art density-functional and genetic-optimization techniques, of the electronic and structural properties of borophene grown on Al(111), with emphasis on the impact of oxygen on the strength of the coupling between substrate and overlayer. While our results confirm the formation of Al-B bonds, they also predict that oxygen doping reduces charge transfer between aluminum and borophene, thus allowing modulation of their strength and paving the way to engineering the electronic properties of 2D-supported borophene sheets for industrial applications. Our study is completed by a thorough study of the thermodynamic stability of the oxygenated borophene-Al(111) interface.

cond-mat.mtrl-sci↗

arXiv2020

Evaluation of molecular orbital symmetry via oxygen-induced charge transfer quenching at a metal-organic interface

Thin molecular films under model conditions are often exploited as benchmarks and case studies to investigate the electronic and structural changes occurring on the surface of metallic electrodes. Here we show that the modification of a metallic surface induced by oxygen adsorption allows the preservation of the geometry of a molecular adlayer, giving access to the determination of molecular orbital symmetries by means of near-edge x-ray absorption fine structure spectroscopy, NEXAFS. As a prototypical example, we exploited Nickel Tetraphenyl Porphyrin molecules deposited on a bare and on an oxygen pre-covered Cu(100) surface. We find that adsorbed atomic oxygen quenches the charge transfer at the metal-organic interface but, in contrast to a thin film sample, maintains the ordered adsorption geometry of the organic molecules. In this way, it is possible to disentangle π* and σ* symmetry orbitals, hence estimating the relative oscillator strength of core level transitions directly from the experimental data, as well as to evaluate and localize the degree of charge transfer in a coupled system. In particular, we neatly single out the σ* contribution associated with the N 1s transition to the mixed N 2px,y-Ni 3dx2-y2 orbital, which falls close to the leading π*-symmetry LUMO resonance.

cond-mat.mtrl-sci↗

arXiv2020

Molecular anchoring stabilizes low valence Ni(I)TPP on copper against thermally induced chemical changes

Many applications of molecular layers deposited on metal surfaces, ranging from single-atom catalysis to on-surface magnetochemistry and biosensing, rely on the use of thermal cycles to regenerate the pristine properties of the system. Thus, understanding the microscopic origin behind the thermal stability of organic/metal interfaces is fundamental for engineering reliable organic-based devices. Here, we study nickel porphyrin molecules on a copper surface as an archetypal system containing a metal center whose oxidation state can be controlled through the interaction with the metal substrate. We demonstrate that the strong molecule-surface interaction, followed by charge transfer at the interface, plays a fundamental role in the thermal stability of the layer by rigidly anchoring the porphyrin to the substrate. Upon thermal treatment, the molecules undergo an irreversible transition at 420 K, which is associated with an increase of the charge transfer from the substrate, mostly localized on the phenyl substituents, and a downward tilting of the latters without any chemical modification

cond-mat.mtrl-sci↗

arXiv2015

Condensation phenomena in fat-tailed distributions: a characterization by means of an order parameter

Condensation phenomena are ubiquitous in nature and are found in condensed matter, disordered systems, networks, finance, etc. In the present work we investigate one of the best frameworks in which condensation phenomena take place, namely, the sum of independent and fat-tailed distributed random variables. For large deviations of the sum, this system undergoes a phase transition and shifts from a democratic phase to a condensed phase, where a single variable (the condensate) carries a finite fraction of the sum. This phenomenon yields the failure of the standard results of the Large Deviation Theory. In this work we exploit the Density Functional Method to overcome the limitation of the Large Deviation Theory and characterize the condensation transition in terms of an order parameter, i.e. the Inverse Participation Ratio (IPR). This procedure leads us to investigate the system in the large-deviation regime where both the sum and the IPR are constrained, observing new phase transitions. As a sample application, the case of condensation phenomena in financial time-series is briefly discussed.

cond-mat.stat-mech↗

arXiv2014

On the concentration of large deviations for fat tailed distributions, with application to financial data

Large deviations for fat tailed distributions, i.e. those that decay slower than exponential, are not only relatively likely, but they also occur in a rather peculiar way where a finite fraction of the whole sample deviation is concentrated on a single variable. The regime of large deviations is separated from the regime of typical fluctuations by a phase transition where the symmetry between the points in the sample is spontaneously broken. For stochastic processes with a fat tailed microscopic noise, this implies that while typical realizations are well described by a diffusion process with continuous sample paths, large deviation paths are typically discontinuous. For eigenvalues of random matrices with fat tailed distributed elements, a large deviation where the trace of the matrix is anomalously large concentrates on just a single eigenvalue, whereas in the thin tailed world the large deviation affects the whole distribution. These results find a natural application to finance. Since the price dynamics of financial stocks is characterized by fat tailed increments, large fluctuations of stock prices are expected to be realized by discrete jumps. Interestingly, we find that large excursions of prices are more likely realized by continuous drifts rather than by discontinuous jumps. Indeed, auto-correlations suppress the concentration of large deviations. Financial covariance matrices also exhibit an anomalously large eigenvalue, the market mode, as compared to the prediction of random matrix theory. We show that this is explained by a large deviation with excess covariance rather than by one with excess volatility.

cond-mat.stat-mech↗