arXiv subjects

Umberto De Giovannini

Publications and source records attributed to Umberto De Giovannini.

At least 55 records · Page 3Linked to original sources

arXiv2019

Octopus, a computational framework for exploring light-driven phenomena and quantum dynamics in extended and finite systems

Over the last years extraordinary advances in experimental and theoretical tools have allowed us to monitor and control matter at short time and atomic scales with a high-degree of precision. An appealing and challenging route towards engineering materials with tailored properties is to find ways to design or selectively manipulate materials, especially at the quantum level. To this end, having a state-of-the-art ab initio computer simulation tool that enables a reliable and accurate simulation of light-induced changes in the physical and chemical properties of complex systems is of utmost importance. The first principles real-space-based Octopus project was born with that idea in mind, providing an unique framework allowing to describe non-equilibrium phenomena in molecular complexes, low dimensional materials, and extended systems by accounting for electronic, ionic, and photon quantum mechanical effects within a generalized time-dependent density functional theory framework. The present article aims to present the new features that have been implemented over the last few years, including technical developments related to performance and massive parallelism. We also describe the major theoretical developments to address ultrafast light-driven processes, like the new theoretical framework of quantum electrodynamics density-functional formalism (QEDFT) for the description of novel light-matter hybrid states. Those advances, and other being released soon as part of the Octopus package, will enable the scientific community to simulate and characterize spatial and time-resolved spectroscopies, ultrafast phenomena in molecules and materials, and new emergent states of matter (QED-materials).

physics.comp-ph↗

arXiv2019

Floquet analysis of excitations in materials

Controlled excitation of materials can transiently induce changed or novel properties with many fundamental and technological implications. Especially, the concept of Floquet engineering, manipulation of the electronic structure via dressing with external lasers, has attracted some recent interest. Here we review the progress made in defining Floquet materials properties and give a special focus on their signatures in experimental observables as well as considering recent experiments realizing Floquet phases in solid state materials. We discuss how a wide range of experiments with non-equilibrium electronic structure can be viewed by employing Floquet theory as an analysis tool providing a different view of excitations in solids.

cond-mat.mtrl-sci↗

arXiv2019

Local Berry curvature signatures in dichroic angle-resolved photoelectron spectroscopy

Topologically nontrivial two-dimensional materials hold great promise for next-generation optoelectronic applications. However, measuring the Hall or spin-Hall response is often a challenge and practically limited to the ground state. An experimental technique for tracing the topological character in a differential fashion would provide useful insights. In this work, we show that circular dichroism angle-resolved photoelectron spectroscopy (ARPES) provides a powerful tool which can resolve the topological and quantum-geometrical character in momentum space. In particular, we investigate how to map out the signatures of the local Berry curvature by exploiting its intimate connection to the orbital angular momentum. A spin-resolved detection of the photoelectrons allows to extend the approach to spin-Chern insulators. Our predictions are corroborated by state-of-the art \emph{ab initio} simulations employing time-dependent density functional theory, complemented with model calculations. The present proposal can be extended to address topological properties in materials out of equilibrium in a time-resolved fashion.

cond-mat.mes-hall↗

arXiv2019

Multiple orbital effects in laser-induced electron diffraction of aligned molecules

Photoelectron Angular Distributions (PADs) resulting from 800 nm and 1300 nm strong field ionization of impulsively aligned CF$_3$I molecules were analyzed using time-dependent density functional theory (TDDFT). The normalized difference between the PADs for aligned and anti-aligned molecules displays large modulations in the high-energy re-collision plateau that are assigned to the diffraction of back-scattered photoelectrons. The TDDFT calculations reveal that, in spite of their 2.6 eV energy difference, ionization from the HOMO-1 orbital contributes to the diffraction pattern on the same footing as ionization from the doubly degenerate HOMO orbital.

physics.chem-ph↗

arXiv2018

Unraveling materials Berry curvature and Chern-Simons numbers from real-time evolution of Bloch states

Materials can be classified by the topological character of their electronic structure and, in this perspective, global attributes immune to local deformations have been discussed in terms of Berry curvature and Chern numbers. Except for instructional simple models, linear response theories have been ubiquitously employed in calculations of topological properties of real materials. Here we propose a completely different and versatile approach to get the topological characteristics of materials by calculating physical observables from the real-time evolving Bloch states: the cell-averaged current density reveals the anomalous velocities whose integration leads to the conductivity quantum. Results for prototypical cases are shown, including a spin-frozen valley-Hall and a quantum anomalous Hall insulator. The advantage of this method is best illustrated by the example of a quantum spin Hall insulator: the quantized spin Hall conductivity is straightforwardly obtained irrespective of the non-Abelian nature in its Berry curvature. Moreover, the method can be extended to the description of real observables in non-equilibrium states of topological materials.

cond-mat.mes-hall↗

arXiv2018

Ab initio simulation of attosecond transient absorption spectroscopy in two-dimensional materials

We extend the first-principles analysis of attosecond transient absorption spectroscopy to two-dimensional materials. As an example of two-dimensional materials, we apply the analysis to monolayer hexagonal boron nitride (h-BN) and compute its transient optical properties under intense few-cycle infrared laser pulses. Nonadiabatic features are observed in the computed transient absorption spectra. To elucidate the microscopic origin of these features, we analyze the electronic structure of h-BN with density functional theory and investigate the dynamics of specific energy bands with a simple two-band model. Finally, we find that laser-induced intraband transitions play a significant role in the transient absorption even for the two-dimensional material and that the nonadiabatic features are induced by the dynamical Franz-Keldysh effect with an anomalous band dispersion.

cond-mat.mtrl-sci↗

arXiv2018

First-principles simulations for attosecond photoelectron spectroscopy based on time-dependent density functional theory

We develop a first-principles simulation method for attosecond time-resolved photoelectron spectroscopy. This method enables us to directly simulate the whole experimental processes, including excitation, emission and detection on equal footing. To examine the performance of the method, we use it to compute the reconstruction of attosecond beating by interference of two-photon transitions (RABBITT) experiments of gas-phase Argon. The computed RABBITT photoionization delay is in very good agreement with recent experimental results from [Klünder et al, Phys. Rev. Lett. 106 143002 (2011)] and [Guénot et al, Phys. Rev. A 85 053424 (2012)]. This indicates the significance of a fully-consistent theoretical treatment of the whole measurement process to properly describe experimental observables in attosecond photoelectron spectroscopy. The present framework opens the path to unravel the microscopic processes underlying RABBITT spectra in more complex materials and nanostructures.

physics.atom-ph↗

arXiv2018

Phonon driven Floquet matter

A resonantly excited coherent phonon leads to a periodic oscillation of the atomic lattice in a crystal structure bringing the material into a non-equilibrium electronic configuration. Periodically oscillating quantum systems can be understood in terms of Floquet theory and we show these concepts can be applied to coherent lattice vibrations reflecting the underlying coupling mechanism between electrons and bosonic modes. This coupling leads to dressed quasi-particles imprinting specific signatures in the spectrum of the electronic structure. Taking graphene as a paradigmatic material we show how the phonon-dressed states display an intricate sideband structure revealing electron-phonon coupling and topological ordering. This work establishes that the recently demonstrated concept of light-induced non-equilibrium Floquet phases can also be applied when using coherent phonon modes for the dynamical control of material properties. The present results are generic for bosonic time-dependent perturbations and similar phenomena can be observed for plasmon, magnon or exciton driven materials.

cond-mat.mtrl-sci↗

arXiv2017

Generation and evolution of spin-, valley- and layer-polarized excited carriers in inversion-symmetric WSe2

Manipulation of spin and valley degrees of freedom is a key step towards realizing novel quantum technologies, for which atomically thin transition metal dichalcogenides (TMDCs) have been established as promising candidates. In monolayer TMDCs, the lack of inversion symmetry gives rise to a spin-valley correlation of the band structure allowing for valley-selective electronic excitation with circularly polarized light. Here we show that, even in centrosymmetric samples of 2H-WSe2, circularly polarized light can generate spin-, valley- and layer-polarized excited states in the conduction band. Employing time- and angle-resolved photoemission spectroscopy (trARPES) with spin-selective excitation, the dynamics of valley and layer pseudospins of the excited carriers are investigated. Complementary time-dependent density functional theory (TDDFT) calculations of the excited state populations reveal a strong circular dichroism of the spin-, valley- and layer-polarizations and a pronounced 2D character of the excited states in the K valleys. We observe scattering of carriers towards the global minimum of the conduction band on a sub-100 femtosecond timescale to states with three-dimensional character facilitating inter-layer charge transfer. Our results establish the optical control of coupled spin-, valley- and layer-polarized states in centrosymmetric materials and suggest the suitability of TMDC multilayer materials for valleytronic and spintronic device concepts.

cond-mat.mes-hall↗

arXiv2016

Monitoring in real time the photon-dressing and undressing of quasiparticles from first principles time-resolved photoelectron spectroscopy

Optical pumping of solids creates a non-equilibrium electronic structure where electrons and photons combine to form quasiparticles of dressed electronic states. The resulting shift of electronic levels is known as the optical Stark effect, visible as a red shift in the optical spectrum. Here we show that in a pump-probe setup we can uniquely define a non-equilibrium quasiparticle bandstructure that can be directly measurable with photo-electron spectroscopy. The dynamical photon-dressing (and undressing) of the many-body electronic states can be monitored by pump-probe time and angular resolved photoelectron spectroscopy (tr-ARPES) as the photon-dressed bandstructure evolves in time depending on the pump-probe pulse overlap. The computed tr-ARPES spectrum agrees perfectly with the quasi-energy spectrum of Floquet theory at maximum overlap and goes to the the equilibrium bandstructure as the pump-probe overlap goes to zero. Additionally, we show how this time-dependent non-equilibrium quasiparticle structure can be understood to be the bandstructure underlying the optical Stark effect. The extension to spin-resolved PES can be used to predict asymmetric dichroic response linked to the valley selective optical excitations in monolayer transition metal dichalcogenides (TMDs).

cond-mat.mtrl-sci↗

arXiv2016

A first principles TDDFT framework for spin and time-resolved ARPES in periodic systems

We present a novel theoretical approach to simulate spin, time and angular-resolved photoelectron spectroscopy (ARPES) from first principles that is applicable to surfaces, thin films, few layer systems, and low-dimensional nanostructures. The method is based on a general formulation in the framework of time-dependent density functional theory (TDDFT) to describe the real time-evolution of electrons escaping from a surface under the effect of any external (arbitrary) laser field. By extending the so called t-SURFF method to periodic systems one can calculate the final photoelectron spectrum by collecting the flux of the ionization current trough an analysing surface. The resulting approach, that we named t-SURFFP, allows to describe a wide range of irradiation conditions without any assumption on the dynamics of the ionization process allowing for pump-probe simulations on an equal footing. To illustrate the wide scope of applicability of the method we present applications to graphene, mono- and bi-layer WSe$_2$, and hexagonal BN under different laser configurations.

physics.comp-ph↗

arXiv2016

Efficient and accurate modeling of electron photoemission in nanostructures with TDDFT

We review different computational methods for the calculation of photoelectron spectra and angular distributions of atoms and molecules when excited by laser pulses using time-dependent density-functional theory (TDDFT) that are suitable for the description of electron emission in compact spatial regions. We derive and extend the time-dependent surface-flux method introduced in Reference [Tao L and Scrinzi A 2012 New Journal of Physics 14 013021] within a TDDFT formalism and compare its performance to other existing methods. We illustrate the performance of the new method by simulating strong-field ionization of C$_{60}$ fullerene and discuss final state effects in the orbital reconstruction of planar organic molecules.

physics.chem-ph↗

arXiv2016

Tailored pump-probe transient spectroscopy with time-dependent density-functional theory: controlling absorption spectra

Recent advances in laser technology allow us to follow electronic motion at its natural time-scale with ultra-fast time resolution, leading the way towards attosecond physics experiments of extreme precision. In this work, we assess the use of tailored pumps in order to enhance (or reduce) some given features of the probe absorption (for example, absorption in the visible range of otherwise transparent samples). This type of manipulation of the system response could be helpful for its full characterization, since it would allow us to visualize transitions that are dark when using unshaped pulses. In order to investigate these possibilities, we perform first a theoretical analysis of the non-equilibrium response function in this context, aided by one simple numerical model of the Hydrogen atom. Then, we proceed to investigate the feasibility of using time-dependent density-functional theory as a means to implement, theoretically, this absorption-optimization idea, for more complex atoms or molecules. We conclude that the proposed idea could in principle be brought to the laboratory: tailored pump pulses can excite systems into light-absorbing states. However, we also highlight the severe numerical and theoretical difficulties posed by the problem: large-scale non-equilibrium quantum dynamics are cumbersome, even with TDDFT, and the shortcomings of state-of-the-art TDDFT functionals may still be serious for these out-of-equilibrium situations.

cond-mat.other↗

arXiv2015

Real-space grids and the Octopus code as tools for the development of new simulation approaches for electronic systems

Real-space grids are a powerful alternative for the simulation of electronic systems. One of the main advantages of the approach is the flexibility and simplicity of working directly in real space where the different fields are discretized on a grid, combined with competitive numerical performance and great potential for parallelization. These properties constitute a great advantage at the time of implementing and testing new physical models. Based on our experience with the Octopus code, in this article we discuss how the real-space approach has allowed for the recent development of new ideas for the simulation of electronic systems. Among these applications are approaches to calculate response properties, modeling of photoemission, optimal control of quantum systems, simulation of plasmonic systems, and the exact solution of the Schrödinger equation for low-dimensionality systems.

physics.chem-ph↗

arXiv2014

Modeling electron dynamics coupled to continuum states in finite volumes

Absorbing boundaries are frequently employed in real-time propagation of the Schrödinger equation to remove spurious reflections and efficiently emulate outgoing boundary conditions. These conditions are a fundamental ingredient for an implicit description of observables involving infinitely extended continuum states. In the literature, several boundary absorbers have been proposed. They mostly fall into three main families: mask function absorbers, complex absorbing potentials, and exterior complex-scaled potentials. To date none of the proposed absorbers is perfect, and all present a certain degree of reflections. Characterization of such reflections is thus a critical task with strong implications for time-dependent simulations of atoms and molecules. We introduce a method to evaluate the reflection properties of a given absorber and present a comparison of selected samples for each family of absorbers. Further, we discuss the connections between members of each family and show how the same reflection curves can be obtained with very different absorption schemes.

physics.comp-ph↗

arXiv2014

Time-Dependent Density-Functional Theory of Strong-Field Ionization of Atoms under Soft X-Rays

We demonstrate the capabilities of time-dependent density functional theory (TDDFT) for strong-field, short wavelength (soft X-ray) physics, as compared to a formalism based on rate equations. We find that TDDFT provides a very good description of the total and individual ionization yields for Ne and Ar atoms exposed to strong laser pulses. We assess the reliability of different adiabatic density functionals and conclude that an accurate description of long-range interactions by the exchange and correlation potential is crucial for obtaining the correct ionization yield over a wide range of intensities ($10^{13}$ -- $5 \times 10^{15}$ W/cm$^2$). Our TDDFT calculations disentangle the contribution from each ionization channel based on the Kohn-Sham wavefunctions.

physics.atm-clus↗

arXiv2014

Modelling the effect of nuclear motion on the attosecond time-resolved photoelectron spectra of ethylene

Using time dependent density functional theory (TDDFT) we examine the energy, angular and time-resolved photoelectron spectra (TRPES) of ethylene in a pump-probe setup. To simulate TRPES we expose ethylene to an ultraviolet (UV) femtosecond pump pulse, followed by a time delayed extreme ultraviolet (XUV) probe pulse. Studying the photoemission spectra as a function of this delay provides us direct access to the dynamic evolution of the molecule's electronic levels. Further, by including the nuclei's motion, we provide direct chemical insight into the chemical reactivity of ethylene. These results show how angular and energy resolved TRPES could be used to directly probe electron and nucleus dynamics in molecules.

physics.atm-clus↗

arXiv2013

Stark Ionization of Atoms and Molecules within Density Functional Resonance Theory

We show that the energetics and lifetimes of resonances of finite systems under an external electric field can be captured by Kohn--Sham density functional theory (DFT) within the formalism of uniform complex scaling. Properties of resonances are calculated self-consistently in terms of complex densities, potentials and wavefunctions using adapted versions of the known algorithms from DFT. We illustrate this new formalism by calculating ionization rates using the complex-scaled local density approximation and exact exchange. We consider a variety of atoms (H, He, Li and Be) as well as the hydrogen molecule. Extensions are briefly discussed.

cond-mat.mtrl-sci↗