In the following, Alessandro Cossard’s publications:
A. Erba, J.K. Desmarais, S. Casassa, B. Civalleri, L. Donà, I. Bush, B. Searle, L. Maschio, L.E. Daga, A. Cossard, C. Ribaldone, E. Ascrizzi, N. Marana, JP. Flament, B. Kirtman, CRYSTAL23: A Program for Computational Solid State Physics and Chemistry, Journal of Chemical Theory and Computation, 2022
Abstract: The Crystal program for quantum-mechanical simulations of materials has been bridging the realm of molecular quantum chemistry to the realm of solid state physics for many years, since its first public version released back in 1988. This peculiarity stems from the use of atom-centered basis functions within a linear combination of atomic orbitals (LCAO) approach and from the corresponding efficiency in the evaluation of the exact Fock exchange series. In particular, this has led to the implementation of a rich variety of hybrid density functional approximations since 1998. Nowadays, it is acknowledged by a broad community of solid state chemists and physicists that the inclusion of a fraction of Fock exchange in the exchange-correlation potential of the density functional theory is key to a better description of many properties of materials (electronic, magnetic, mechanical, spintronic, lattice-dynamical, etc.). Here, the main developments made to the program in the last five years (i.e., since the previous release, Crystal17) are presented and some of their most noteworthy applications reviewed.
A. Cossard, S. Casassa, C. Gatti, J.K. Desmarais, A. Erba, Topology of the Electron Density and of Its Laplacian from Periodic LCAO Calculations on f-Electron Materials: The Case of Cesium Uranyl Chloride, Molecules 26 (14), 4227, 2021
Abstract: The chemistry of f-electrons in lanthanide and actinide materials is yet to be fully rationalized. Quantum-mechanical simulations can provide useful complementary insight to that obtained from experiments. The quantum theory of atoms in molecules and crystals (QTAIMAC), through thorough topological analysis of the electron density (often complemented by that of its Laplacian) constitutes a general and robust theoretical framework to analyze chemical bonding features from a computed wave function. Here, we present the extension of the Topond module (previously limited to work in terms of s-, p– and d-type basis functions only) of the Crystal program to f– and g-type basis functions within the linear combination of atomic orbitals (LCAO) approach. This allows for an effective QTAIMAC analysis of chemical bonding of lanthanide and actinide materials. The new implemented algorithms are applied to the analysis of the spatial distribution of the electron density and its Laplacian of the cesium uranyl chloride, Cs2UO2Cl4, crystal. Discrepancies between the present theoretical description of chemical bonding and that obtained from a previously reconstructed electron density by experimental X-ray diffraction are illustrated and discussed.
A. Cossard, J.K. Desmarais, S. Casassa, C. Gatti, A. Erba, Charge Density Analysis of Actinide Compounds from the Quantum Theory of Atoms in Molecules and Crystals, The Journal of Physical Chemistry Letters 12 (7), 1862-1868, 2021
Abstract: The nature of chemical bonding in actinide compounds (molecular complexes and materials) remains elusive in many respects. A thorough analysis of their electron charge distribution can prove decisive in elucidating bonding trends and oxidation states along the series. However, the accurate determination and robust analysis of the charge density of actinide compounds pose several challenges from both experimental and theoretical perspectives. Significant advances have recently been made on the experimental reconstruction and topological analysis of the charge density of actinide materials [Gianopoulos et al. IUCrJ, 2019, 6, 895]. Here, we discuss complementary advances on the theoretical side, which allow for the accurate determination of the charge density of actinide materials from quantum-mechanical simulations in the bulk. In particular, the extension of the Topond software implementing Bader’s quantum theory of atoms in molecules and crystals (QTAIMAC) to f– and g-type basis functions is introduced, which allows for an effective study of lanthanides and actinides in the bulk and in vacuo, on the same grounds. Chemical bonding of the tetraphenyl phosphate uranium hexafluoride cocrystal [PPh4+][UF6–] is investigated, whose experimental charge density is available for comparison. Crystal packing effects on the charge density and chemical bonding are quantified and discussed. The methodology presented here allows reproducing all subtle features of the topology of the Laplacian of the experimental charge density. Such a remarkable qualitative and quantitative agreement represents a strong mutual validation of both approaches—experimental and computational—for charge density analysis of actinide compounds.
A. Cossard, G. De Francisci Morales, Y. Mejova, K. Kalimeri K, D. Paolotti, M. Starnini, Falling into the echo-chamber: the Italian vaccination debate on Twitter, Contribution to the 14th International Conference on Web and Social Media, 2020
Abstract: The reappearance of measles in the US and Europe, a disease considered eliminated in early 2000s, has been accompanied by a growing debate on the merits of vaccination on social media. In this study we examine the extent to which the vaccination debate on Twitter is conductive to potential outreach to the vaccination hesitant. We focus on Italy, one of the countries most affected by the latest measles outbreaks. We discover that the vaccination skeptics, as well as the advocates, reside in their own distinct “echo chambers”. The structure of these communities differs as well, with skeptics arranged in a tightly connected cluster, and advocates organizing themselves around few authoritative hubs. At the center of these echo chambers we find the ardent supporters, for which we build highly accurate network-and content-based classifiers (attaining 95% cross-validated accuracy). Insights of this study provide several avenues for potential future interventions, including network-guided targeting, accounting for the political context, and monitoring of alternative sources of information.
M. De Stefanis, C. Ravoux, A Cossard, A. Erba, Thermo-elasticity of Materials from Quasi-Harmonic calculation, Minerals, 9, 16, 2018. Featured front cover journal paper.
Abstract: An effective algorithm for the quasi-harmonic calculation of thermo-elastic stiffness constants of materials is discussed and implemented into the Crystal program for quantum-mechanical simulations of extended systems. Two different approaches of increasing complexity and accuracy are presented. The first one is a quasi-static approximation where the thermal dependence of elastic constants is assumed to be due only to the thermal expansion of the system. The second one is fully quasi-harmonic, takes into account thermal expansion, and explicitly computes Helmholtz free energy derivatives with respect to strain. The conversion of isothermal into adiabatic thermo-elastic constants is also addressed. The algorithm is formally presented and applied to the description of the thermo-elastic response of the forsterite mineral.