arXiv subjects

Maurizio Benfatto

Publications and source records attributed to Maurizio Benfatto.

5 recordsLinked to original sources

arXiv2026

Configuration averaging of X-ray absorption spectra of disordered systems within the augmented-space full multiple-scattering formalism

We present a formulation of the full multiple-scattering theory of X-ray absorption spectroscopy (XAS) for disordered systems based on the augmented-space method of Mookerjee. Both substitutional (chemical) and thermal (vibrational) disorder are cast, on the same footing, as exact matrix elements of a non-random operator acting on an enlarged Hilbert space. The configuration-averaged scattering-path operator is thereby obtained by inverting a non-random secular matrix, with no expansion in scattering paths, without recourse to the single-site approximation and without any assumption on the shape of the disorder distribution. This is what the quantitative analysis of the near-edge region requires: XANES lies where the multiple-scattering series does not converge, so that a treatment of disorder tied to a path expansion is unavailable there. The inversion is carried out by a continued-fraction (Lanczos) recursion, which accesses the required matrix element without constructing the full configuration basis or diagonalising the augmented operator. The operator Debye-Waller factor of the harmonic theory is recovered as the Gaussian special case, and anharmonic disorder is included with no additional machinery, through the moments of a non-Gaussian displacement distribution. Where the series does converge, the construction also settles a question of principle: for statistically independent site variables, replacing each t-matrix by its configuration average is exact only for scattering paths in which every site occurs once, and for paths that revisit a site we obtain the exact second-order correction.

cond-mat.mtrl-sci↗

arXiv2015

Watching coherent molecular structural dynamics during photoreaction: beyond kinetic description

A deep understanding of molecular photo-transformations is challenging because of the complex interaction between the configurations of electrons and nuclei. An initial optical excitation dissipates energy into electronic and structural degrees of freedom, often in less than one trillionth (10^-12) of a second. Molecular dynamics induced by photoexcitation have been very successfully studied with femtosecond optical spectroscopies, but electronic and nuclear dynamics are often very difficult to disentangle. X-ray based spectroscopies can reduce the ambiguity between theoretical models and experimental data, but it is only with the recent development of bright ultrafast X-ray sources, that key information during transient molecular processes can be obtained on their intrinsic timescale. In this letter, Free Electron Laser (FEL) radiation is used to measure ultrafast changes in the X-ray Absorption Near Edge Structure (XANES) during the prototypical photoreaction of a spin crossover compound. We reveal its transformation from the ligand-located electronic photoexcitation to the structural trapping of the high spin state. The results require a description beyond a kinetic model and provide a direct observation of a dynamic breathing of the main structural change. The coherent structural oscillations (period of ~265 fs) in the photoproduct potential lose synchrony within ~330 fs, whereas incoherent motions reveal the energy redistribution and vibrational cooling within ~1.6 ps. We foresee that ultrafast X-ray spectroscopies will provide invaluable insight to understand the complex physics of fundamental light induced phenomena, which are of prime interest in a multitude of chemical, physical and biological processes.

physics.chem-ph↗

arXiv2010

Full-Potential Multiple Scattering Theory with Space-Filling Cells for bound and continuum states

We present a rigorous derivation of a real space Full-Potential Multiple-Scattering-Theory (FP-MST), valid both for continuum and bound states, that is free from the drawbacks that up to now have impaired its development, in particular the need to use cell shape functions and rectangular matrices. In this connection we give a new scheme to generate local basis functions for the truncated potential cells that is simple, fast, efficient, valid for any shape of the cell and reduces to the minimum the number of spherical harmonics in the expansion of the scattering wave function. The method also avoids the need for saturating 'internal sums' due to the re-expansion of the spherical Hankel functions around another point in space (usually another cell center). Thus this approach, provides a straightforward extension of MST in the Muffin-Tin (MT) approximation, with only one truncation parameter given by the classical relation $l_{\rm max} = kR_b$, where $k$ is the excited (or ground state) electron wave vector and $R_b$ the radius of the bounding sphere of the scattering cell. It is shown that the theory converges absolutely in the $l_{\rm max} \to \infty$ limit. As a consequence it provides a firm ground to the use of FP-MST as a viable method for electronic structure calculations and makes possible the computation of x-ray spectroscopies, notably photo-electron diffraction, absorption and anomalous scattering among others, with the ease and versatility of the corresponding MT theory. Some numerical applications of the theory are presented, both for continuum and bound states.

cond-mat.other↗

arXiv2008

Full Potential Multiple Scattering for X-ray Spectroscopies

We present a Full Potential Multiple Scattering (FP-MS) scheme for the interpretation of several X-ray spectroscopies that is a straightforward generalization of the more conventional Muffin-Tin (MT) version. Like this latter, it preserves the intuitive description of the physical process under consideration and overcomes some of the limitations of the existing FP-MS codes. It hinges on a fast and efficient method for solving the single cell scattering problem that avoids the convergence drawbacks of the angular momentum (AM) expansion of the cell shape function and relies on an alternative derivation of the multiple scattering equations (MSE) that allows us to work reliably with only one truncation parameter, {\it i.e.} the number of local basis functions in the expansion of the global scattering function determined by the classical relation $l_{\rm max} \sim k R$.

cond-mat.mtrl-sci↗

arXiv1997

X-Ray Resonant Scattering as a Direct Probe of Orbital Ordering in Transition-Metal Oxides

X-ray resonant scattering at the K-edge of transition metal oxides is shown to measure the orbital order parameter, supposed to accompany magnetic ordering in some cases. Virtual transitions to the 3d-orbitals are quadrupolar in general. In cases with no inversion symmetry, such as V$_2$O$_3$, treated in detail here, a dipole component enhances the resonance. Hence, we argue that the detailed structure of orbital order in V$_2$O$_3$ is experimentally accessible.

cond-mat.str-el↗