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The Tully’s fewest switches surface hopping algorithm is implemented within the framework of the time-dependent density functional based tight binding method (TD-DFTB) to simulate the energy relaxation following absorption of a UV photon by polycyclic aromatic hydrocarbons (PAHs). This approach is used to study the size effect on the ultrafast dynamics in excited states for a special class of PAH species called polyacenes. We determine the dynamical relaxation times and discuss the underlying mechanisms. Our results show that there is a striking alternation in decay times of the brightest singlet state for neutral polyacenes with 3 to 6 aromatic cycles. The alternation corresponds to an order-of-magnitude variation between roughly 10 and 100 fs and is correlated with a qualitatively similar alternation of energy gaps between the brightest state and the state lying just below in energy.

We have studied the dynamic evolution of a Cs atom photo-excited from 6s to 6p and 7s states on a helium droplet using time-dependent 4He-DFT simulations. Depending on the excited electronic state, the Cs impurity remains on the droplet surface or it is ejected. Upon subsequent photo-ionization of the excited Cs atom the resulting Cs+ cation may either be ejected or come back to the droplet, depending on the time delay between photo-excitation and photo-ionization. We have calculated the critical time delay separating these two different behaviors, as well as final ion velocities. These observables will be used for future comparison with planned pump-probe experiments.

The vibrational predissociation of NeBr2 has been studied using a variety of theoretical and experimental methods, producing a large number of results. It is therefore a useful system for comparing different theoretical methods. Here, we apply the trajectory surface hopping (TSH) method that consists of propagating the dynamics of the system on a potential energy surface (PES) corresponding to quantum molecular vibrational states with possibility of hopping towards other surfaces until the van der Waals bond dissociates. This allows quantum vibrational effects to be added to a classical dynamics approach. We have also incorporated the kinetic mechanism for a better compression of the evolution of the complex. The novelty of this work is that it allows us to incorporate all the surfaces for (v = 16, 17,. .. , 29) into the dynamics of the system. The calculated lifetimes are similar to those previously reported experimentally and theoretically. The rotational distribution, the rotational energy and j max are in agreement with other works, providing new information for this complex.

Light absorption or fluorescence excitation spectroscopy of alkali atoms attached to 4He droplets is investigated as a possible way for detecting the presence of vortices. To this end, we have calculated the equilibrium configuration and energetics of alkali atoms attached to a 4He1000 droplet hosting a vortex line using 4He density functional theory. We use them to study how the dipole absorption spectrum of the alkali atom is modified when the impurity is attached to a vortex line. Spectra are found to be blue-shifted (higher frequencies) and broadened compared to vortex-free droplets because the dimple in which the alkali atom sits at the intersection of the vortex line and the droplet surface is deeper. This effect is smaller for lighter alkali atoms and all the more so when using a quantum description since, in this case, they sit further away from the droplet surface on average due to their zero-point motion. Spectral modifications due to the presence of a vortex line are minor for np ← ns excitation and therefore insufficient for vortex detection. In the case of higher n′ p ← ns or n′ s ← ns (n′ > n) excitations, the shifts are larger as the excited state orbital is more extended and therefore more sensitive to changes in the surrounding helium density.

¡¡¡¡¡¡¡ HEAD The scopeρ of this article is to present an overview of the Density Functional based Tight Binding (DFTB) method and its applications. The paper introduces the basics of DFTB and its standard formulation up to second order. It also addresses methodological developments such as third order expansion, inclusion of non-covalent interactions, Long-range short range separation to solve the self-interaction error, developments for excited states via the Time-dependent DFTB scheme, inclusion of DFTB in hybrid high-level/low level schemes (DFT/DFTB or DFTB/MM), fragment decomposition of large systems, large scale potential energy landscape exploration with molecular dynamics in ground or excited states, excited states non-adiabatic dynamics. A number of applications are reviewed, focusing on-(i)-the variety of systems that have been studied ======= The scope of this article is to present an overview of the Density Functional based Tight Binding (DFTB) method and its applications. The paper introduces the basics of DFTB and its standard formulation up to second order. It also addresses methodological developments such as third order expansion, inclusion of non-covalent interactions, schemes to solve the self-interaction error, implementation of long-range short-range separation , treatment of excited states via the time-dependent DFTB scheme, inclusion of DFTB in hybrid high-level/low level schemes (DFT/DFTB or DFTB/MM), fragment decomposition of large systems, large scale potential energy landscape exploration with molecular dynamics in ground or excited states, non-adiabatic dynamics. A number of applications are reviewed, focusing on-(i)-the variety of systems that have been studied ¿¿¿¿¿¿¿ f70d2388346dfe2c2221fafac6c2d19fb13b68b9 such as small molecules, large molecules and biomolecules, bare or functionalized clusters, supported or embedded systems, and-(ii)-properties and processes, such as vi-brational spectroscopy, collisions, fragmentation, thermodynamics or non-adiabatic dynamics. Finally outlines and perspectives are given.

The paper presents the first implementation of the row-orthonormal hyperspherical coordinate formalism for the computation of the vibrational spectrum of a tetratomic system. The wavefunc-tion of Ne 4 is expanded on a large basis set of hyperspherical harmonics generated numerically. This method not only provides spectra with reasonable accuracy, but also gives physical insight into the vibrational dynamics of the system. The characteristics of the spectra are related to the symmetry and localization of the wavefunction in configuration space.

The fragmentation upon electron impact ionization of Ar4He1000 is investigated by means of mixed quantum-classical dynamics simulations. The Ar4+ dopant dynamics is described by a surface hopping method coupled with a diatomics-in-molecules model to properly take into account the multiple Ar4+ electronic surfaces and possible transitions between them. Helium atoms are treated individually using the zero-point averaged dynamics (ZPAD), a method based on the building of an effective He-He potential. Fast electronic relaxation is observed, from less than 2 ps to ∼ 30 ps depending on initial conditions. The main fragments observed are Ar2+Heq and Ar3+Heq (q ≤ 1000), with a strong contribution of the bare Ar2+ ion, and neither Ar+ nor Ar+Heq fragments are found. The smaller fragments (q ≤ 50) are found to mostly come from ion ejection whereas larger fragments (q > 500) originate from long-term ion trapping. Although the structure of the trapped Ar2+ ions is the same as in the gas phase, trapped Ar3+ and Ar4+ are rather slightly bound Ar2+ · · · Ar and Ar2+ · · · Ar · · · Ar structures (i.e., an Ar2+ core with one or two argon atoms roaming within the droplet). These loose structures can undergo geminate recombination and release Ar3+Heq or Ar4+Heq (q ≤ 50) in the gas phase and/or induce strong helium droplet evaporation. Finally, the translational energy of the fragment center of mass was found suitable to provide a clear signature of the broad variety of processes at play in our simulations.

In this paper, we report on numerical calculations of the spontaneous emission rates and Lamb shifts of a $^{87}\text{Rb}$ atom in a Rydberg-excited state $\left(n\leq30\right)$ located close to a silica optical nanofiber. We investigate how these quantities depend on the fiber's radius, the distance of the atom to the fiber, the direction of the atomic angular momentum polarization as well as the different atomic quantum numbers. We also study the contribution of quadrupolar transitions, which may be substantial for highly polarizable Rydberg states. Our calculations are performed in the macroscopic quantum electrodynamics formalism, based on the dyadic Green's function method. This allows us to take dispersive and absorptive characteristics of silica into account; this is of major importance since Rydberg atoms emit along many different transitions whose frequencies cover a wide range of the electromagnetic spectrum. Our work is an important initial step towards building a Rydberg atom-nanofiber interface for quantum optics and quantum information purposes.

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We report on numerical simulations demonstrating the emergence of stroboscopic thermalisation in a chain of atoms submitted to a laser eld whose frequency is periodically modulated close to resonance with a transition towards a Rydberg state. We relate the conditions of equilibration of the Rydberg population to the spectrum of the Floquet Hamiltonian and suggest a possible experimental implementation.

Non-adiabatic molecular dynamics of neutral chrysene and tetracene molecules is investigated using Tully’s fewest switches surface hopping algorithm coupled to the time-dependent density functional based tight-binding (TD-DFTB) method for electronic structure calculations. We first assess the performance of two DFTB parameter sets based on the computed TD-DFTB absorption spectra. The main focus is given to the analysis of the electronic relaxation from the brightest excited state following absorption of a UV photon. We determine the dynamical relaxation times and discuss the underlying mechanisms. Our results show that the electronic population of the brightest excited singlet state in armchair-edge chrysene decays an order-of-magnitude faster than the one in zigzag-edge tetracene. This is correlated with a qualitatively similar difference of energy gaps between the brightest state and the state lying just below in energy, which is also consistent with our previous study on polyacenes.

Since the signature of the ITER treaty in 2006, a new research programme targeting the emergence of a new generation of Neutral Beam (NB) system for the future fusion reactor (DEMO Tokamak) has been underway between several laboratories in Europe. The specifications required to operate a NB system on DEMO are very demanding: the system has to provide plasma heating, current drive and plasma control at a very high level of power (up to 150 MW) and energy (1 or 2 MeV), including high performances in term of wall-plug efficiency (η > 60%), high availability and reliability. To this aim, a novel NB concept based on the photodetachment of the energetic negative ion beam is under study. The keystone of this new concept is the achievement of a photoneutralizer where a high power photon flux (~3 MW) generated within a Fabry Perot cavity will overlap, cross and partially photodetach the intense negative ion beam accelerated at high energy (1 or 2 MeV). The aspect ratio of the beam-line (source, accelerator, etc.) is specifically designed to maximize the overlap of the photon beam with the ion beam. It is shown that such a photoneutralized based NB system would have the capability to provide several tens of MW of D 0 per beam line with a wall-plug efficiency higher than 60%. A feasibility study of the concept has been launched between different laboratories to address the different physics aspects, i.e., negative ion source, plasma modelling, ion accelerator simulation, photoneutralization and high voltage holding under vacuum. The paper describes the present status of the project and the main achievements of the developments in laboratories.

Engineering and harnessing coherent excitonic transport in organic nanostructures has recently been suggested as a promising way towards improving manmade light-harvesting materials. However, realizing and testing the dissipative system-environment models underlying these proposals is presently very challenging in supramolec-ular materials. A promising alternative is to use simpler and highly tunable "quantum simulators" built from programmable qubits, as recently achieved in a superconducting circuit by Potočnik et al. [A. Potočnik et al., Nat. Commun. 9, 904 (2018)]. We simulate the real-time dynamics of an exciton coupled to a quantum bath as it moves through a network based on the quantum circuit of Potočnik et al. Using the numerically exact hierarchical equations of motion to capture the open quantum system dynamics, we find that an ultrafast but completely incoherent relaxation from a high-lying "bright" exciton into a doublet of closely spaced "dark" excitons can spontaneously generate electronic coherences and oscillatory real-space motion across the network (quantum beats). Importantly, we show that this behavior also survives when the environmental noise is classically stochastic (effectively high temperature), as in present experiments. These predictions highlight the possibilities of designing matched electronic and spectral noise structures for robust coherence generation that do not require coherent excitation or cold environments.

We propose several quantum mechanical models to describe electronic field emission from first principles. These models allow to correlate quantitatively the electronic emission current to the electrode surface details at the atomic scale. They all rely on electronic potential energie surfaces obtained from three dimensional density functional theory calculations. They differ by the various quantum mechanical methods (exact or perturbative, time dependent or time independent) which are used to describe tunneling through the electronic potential energy barrier. Comparison of these models between them and with the standard Fowler-Nordheim one in the context of one dimensional tunneling allows to assess the impact on the accuracy of the computed current of the approximations made in each model. Among these methods, the time dependent perturbative one provides a well balanced trade-off between accuracy and computational cost.

The effect of metallic surface contamination on field electron emission is investigated for the first time using a three dimensional quantum mechanical model. The plane wave periodic version of the density functional theory is used to obtain wavefunctions and potentials. Local and averaged emitted current densities are obtained from them using time dependent perturbation theory. This method is used to study the effect of the presence of carbon adsorbates on emission from tungsten surfaces. Fowler-Nordheim plots which provide the dependence of the emitted current with the external electric field show that carbon contamination inhibits emission. Significant differences with the results of the analytical Fowler-Nordheim model are observed. Emissions images (i. e. the spatial dependence of the emitted current density) are presented to identify the important emission spots. These images are significantly different from the electronic density plots usually presented to model constant height scanning tunnelling microscope images. Analysis of the emitted current density energy distributions in the light of the projected local density of states provides a deeper understanding of the emission process.

CLASSICAL TRAJECTORY METHOD Quantum dynamics Dynamique moléculaire quantique Effets isotopiques ELECTRONIC BUBBLE FORMATION ENERGY COMPLEX ABSORBING POTENTIALS MODEL Coordonnées hypersphériques elliptiques DEPENDENT SCHRODINGER-EQUATION Agrégats ATOMS Alkali-halide Effets transitoires ELECTRON-NUCLEAR DYNAMICS AR Dark energy Muonic hydrogen Calcium Théorie de la fonctionnelle de la densité Electrostatic accelerators CAVITY Half revival CHEMICAL-REACTIONS ENTANGLEMENT Non-equilibrium Green's function Theory Dynamique mixte classique Molecules STATE Transitions non-adiabatiques Coulomb presssure Effets de propagation Density functional theory Rydberg atoms Cluster WAVE-PACKET DYNAMICS Photophysics Drops Dynamique non-adiabatique Transport électronique Collisions des atomes Collision frequency Composés organiques à valence mixte COHERENT CONTROL DRIVEN Dissipative quantum methods MCTDH Atomic collisions ELECTRON DYNAMICS Slow light Fonction de Green hors-équilibre Effets inélastiques Electronic Structure Electronic transport inelastic effects Atomic clusters Cesium Electric field DYNAMICS Electron-surface collision Bohmian trajectories Ab initio calculations Anharmonicity DFTB Dissipative dynamics CONICAL INTERSECTION DIFFERENTIAL CROSS-SECTIONS Dynamique quantique Clusters Close-coupling QUANTUM OPTIMAL-CONTROL Dynamics ENTROPY Wave packet interferences Collisions ultra froides COLLISION ENERGY Ejection Deformation Cryptochrome Casimir effect DENSITY DISSIPATION Cosmological constant Electron transfer Ultrashort pulses Tetrathiafulvalene Excitation energy transfer EET Contrôle cohérent DEMO Cope rearrangement Propagation effects Energy spectrum Classical trajectory 4He-TDDFT simulation Coherent control Excited states Ab-initio Diels-Alder reaction ALGORITHM Extra dimension