First-principles calculations of heat capacities of ultrafast laser-excited electrons in metals

Ultrafast laser excitation can induce fast increases of the electronic subsystem temperature. The subsequent electronic evolutions in terms of band structure and energy distribution can determine the change of several thermodynamic properties, including one essential for energy deposition; the electronic heat capacity. Using density functional calculations performed at finite electronic temperatures, the electronic heat capacities dependent on electronic temperatures are obtained for a series of metals, including free electron like, transition and noble metals. The effect of exchange and correlation functionals and the presence of semicore electrons on electronic heat capacities are first evaluated and found to be negligible in most cases. Then, we tested the validity of the free electron approaches, varying the number of free electrons per atom. This shows that only simple metals can be correctly fitted with these approaches. For transition metals, the presence of localized d electrons produces a strong deviation toward high energies of the electronic heat capacities, implying that more energy is needed to thermally excite them, compared to free sp electrons. This is attributed to collective excitation effects strengthened by a change of the electronic screening at high temperature

Ultrafast Surface Plasmonic Switch in Non-Plasmonic Metals

We demonstrate that ultrafast carrier excitation can drastically affect electronic structures and induce brief surface plasmonic response in non-plasmonic metals, potentially creating a plasmonic switch. Using first-principles molecular dynamics and Kubo-Greenwood formalism for laser-excited tungsten we show that carrier heating mobilizes d electrons into collective inter and intraband transitions leading to a sign flip in the imaginary optical conductivity, activating plasmonic properties for the initial non-plasmonic phase. The drive for the optical evolution can be visualized as an increasingly damped quasi-resonance at visible frequencies for pumping carriers across a chemical potential located in a d-band pseudo-gap with energy-dependent degree of occupation. The subsequent evolution of optical indices for the excited material is confirmed by time-resolved ultrafast ellipsometry. The large optical tunability extends the existence spectral domain of surface plasmons in ranges typically claimed in laser self-organized nanostructuring. Non-equilibrium heating is thus a strong factor for engineering optical control of evanescent excitation waves, particularly important in laser nanostructuring strategies

Etude théorique du matériau BaSnO₃, en tant que conducteur protonique pour électrolytes de piles à combustible

The present work consist in a theoretical study of the BaSnO3 compound as a protonic conductor for fuel cell electrolytes. These materials are obtained after an aliovalent doping stage that will create oxygen vacancies on the oxygen sublattice of the compound. Then, in a moist atmosphere, this lacunar material is going to hydrate: water molecule will be dissociated, creating protonic defects inside of the compound. The main desired property is the protonic conduction, which is due to two major contributions: number of charge careers (hydrogen or proton coming from the hydration reaction) and their mobility, at a given temperature. These two parameters are quantified by a thermodynamic quantity (hydration enthalpy) and a kinetic parameter (activation energy), which are known to be dependant on the dopant concentration. Thus, a systematic study has been done for the material doped Ga, In, Y, Gd, Sm and La on the Sn site. The objectives of this study were, first, to compute the key parameters of the protonic conduction and to compare them to the experimental data, and, in second, to correlate the calculated results to structural effect due to the dopants, in order to understand how they influence the conduction parameters. To determine these parameters, calculations based on the Density Functional Theory in the GGA-PBE form were carried out, using two different codes: ABINIT and SIESTA. Computations were done for dopant concentrations going from 12.5% to 3.7%, the BaTiO3 compound were also studied. Interesting results were also obtained, from a structural point of view, and concerning dopant local environment. Were evidenced: i. Prefential stabilization of defects, relatively to electrostatic interaction considerations. ii. The dopant concentration effect on dopant-defect (oxygen vacancy and proton) interactions. iii. A dopant size effect which acts in particular in the case of big dopants and which stabilize an other defect position than the one favoured by electrostatic considerations.Les travaux effectués ont consisté en une étude théorique du matériau BaSnO3 en tant que matériau conducteur protonique pour électrolytes de piles à combustible. Ces matériaux sont obtenus après un dopage aliovalent préalable qui génère des lacunes d'oxygène sur le sous-réseau d'oxygène du matériau. Ce matériau, placé en milieu humide va s'hydrater, c'est à dire que des molécules d'eau vont se dissocier au sein du matériau. La propriété principale souhaitée pour de tels matériaux est la conductivité protonique. Celle-ci dépend du nombre de porteurs de charges (les hydrogènes ou protons apportés par les molécules d'eau) et de leur mobilité. Ces deux paramètres sont quantifiés par des grandeurs thermodynamiques (l'enthalpies d'hydratation) et cinétiques (énergies d'activation) qui peuvent dépendre très fortement des dopants et de leur concentration. Une étude systématique a donc été entreprise sur ce matériau dopé par Ga, In, Y, Gd, Sm et La sur le site du Sn. Les objectifs étaient, d'une part de déterminer les paramètres clés de la conduction protonique et de les comparer aux données expérimentales, et d'autre part de corréler ces informations énergétiques aux effets structuraux imputables aux dopants, dans le but de comprendre comment ces derniers influencent la conduction. Pour remonter à ces paramètres, des calculs basés sur la Théorie de la Fonctionnelle de la Densité ont été réalisés dans l'approximation GGA-PBE, par l'intermédiaire de deux codes de calculs différents: ABINIT et SIESTA. Les calculs ont été menés à la fois à des concentrations de 12,5% et de 3,7% de dopants et le matériau BaTiO3 a également été étudié. D'intéressants résultats ont étés obtenus, notamment d'un point de vue structural, avec l'analyse des déformations locales aux alentours des dopants. Ont été mis en évidence: i. La stabilisation préférentielle de certaines positions des défauts due aux interactions électrostatiques. ii. L'effet de la concentration des dopants sur les énergies d'interaction entre dopant et défauts (lacune d'oxygène et proton) et iii. Un effet de taille de dopant, perceptible notamment dans le cas des gros dopants, et qui stabilise préférentiellement une autre position que celle favorisée d'un point de vue électrostatique

First-principles assessment of potential ultrafast laser-induced structural transition in Ni

International audienceThe possibility to trigger ultrafast solid-to-solid transitions in transition metals under femtosecond laser irradiation is investigated by means of first-principles calculations. Electronic heating can drastically modify screening, charge distribution and atomic binding features, potentially determining new structural relaxation paths in the solid phase, before thermodynamic solid-to-liquid transformations set in. Consequently, we evaluate here the effect of electronic excitation on structural stability and conditions for structural transitions. Ni is chosen as a case study for the probability of a solid transition, and the stability of its FCC phase is compared to the non-standard HCP structure while accounting for the heating of the electronic subsystem. From a phonon spectra analysis, we show that the thermodynamic stability order reverses at an electronic temperature of around 10 4 K. Both structures exhibit a dynamic stability, indicating they present a metastability depending on the heating. However, the general hardening of phonon modes with the increase of the electronic temperature points out that no transformation will occur, as confirmed by the study of a typical FCC to HCP diffusionless transformation path, showing an increasing energy barrier. Finally, based on electronic density of states interpretation, the tendency of different metal categories to undergo or not an ultrafast laser-induced structural transition is discussed

Free-electron properties of metals under ultrafast laser-induced electron-phonon nonequilibrium: A first-principles study

International audienceThe electronic behavior of various solid metals (Al, Ni, Cu, Au, Ti, and W) under ultrashort laser irradiation is investigated by means of density functional theory. Successive stages of extreme nonequilibrium on picosecond time scale impact the excited material properties in terms of optical coupling and transport characteristics. As these are generally modelled based on the free-electron classical theory, the free-electron number is a key parameter. However, this parameter remains unclearly defined and dependencies on the electronic temperature are not considered. Here, from first-principles calculations, density of states are obtained with respect to electronic temperatures varying from 10^-2 to 10^5 K within a cold lattice. Based on the concept of localized or delocalized electronic states, temperature dependent free-electron numbers are evaluated for a series of metals covering a large range of electronic configurations. With the increase of the electronic temperature we observe strong adjustments of the electronic structures of transition metals. These are related to variations of electronic occupation in localized d bands, via change in electronic screening and electron-ion effective potential. The electronic temperature dependence of nonequilibrium density of states has consequences on electronic chemical potentials, free-electron numbers, electronic heat capacities, and electronic pressures. Thus electronic thermodynamic properties are computed and discussed, serving as a base to derive energetic and transport properties allowing the description of excitation and relaxation phenomena caused by rapid laser action

Ab Initio Nonequilibrium Thermodynamic and Transport Properties of Ultrafast Laser Irradiated 316L Stainless Steel

International audienceWe present calculations of transient behavior of thermodynamic and transport coefficients on the timescale of electron-phonon relaxation upon ultrashort laser excitation of ferrous alloys. Their role defining energy deposition and primary microscopic material response to the laser irradiation is outlined. Nonequilib-rium thermodynamic properties of 316L stainless steel are determined from first-principles calculations. Taking into account the complexity of multi-metallic materials, the density functional theory is first applied to describe the electronic density of states of an alloy stainless steel matrix as a function of electronic heating. An increase of the localization degree of the charge density was found to be responsible for the modification of the electronic structure upon electronic heating, with consequences on chemical potential, electronic capacity and pressure. It is shown that the electronic temperature dependence of stainless steel thermo-dynamic properties are consistent with the behavior observed for pure γ-Fe, outlining the role of the main constituent in the same atomic arrangement. Assuming that similar behaviors extend to the transport properties, the transient electron-phonon coupling, optical properties and thermal conductivities of γ-Fe are derived based on density functional perturbation theory and ab initio molecular dynamics and extrapolated for steel. The insertion of accurate transport coefficients allows to improve current models and to achieve more realistic description of femtosecond pulse laser processing. Effects of fast temperature variation driving phase transitions and strong thermal stresses induced by the laser pulse are finally presented by combining first principle results to a nonequilibrium hydrodynamic approach

Unstable polar mode and minium of the dielectric constant in cubic BaSnO3_3 under hydrostatic pressure

From first-principles density-functional theory calculations, we show that above a given hydrostatic pressure, an unstable TO mode appears in the cubic perovskite barium stannate (BaSnO3) at Γ. Below this critical pressure, we predict an interesting lowering of the dielectric response of this compound due to a change in the sign of this TO mode effective charge. The results are compared to recent calculations on perovskites under high pressure (titanates, zirconates, and niobates), which exhibit a different mechanism at the origin of the soft mode, and to magnesium silicate (MgSiO3) that does not undergo any ferroelectric transition under hydrostatic pressure