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Quantum tunneling rotors in a zeolitic imidazolate framework ZIF-8 can provide insights into local gas adsorption sites and local dynamics of porous structure, which are inaccessible to standard physisorption or x-ray diffraction sensitive primarily to long-range order. Using in situ high-resolution inelastic neutron scattering at 3 K, we follow the evolution of methyl tunneling with respect to the number of dosed gas molecules. While nitrogen adsorption decreases the energy of the tunneling peak, and ultimately hinders it completely (0.33 meV to zero), argon substantially increases the energy to 0.42 meV. Ab initio calculations of the rotational barrier of ZIF-8 show an exception to the reported adsorption sites hierarchy, resulting in anomalous adsorption behavior and linker dynamics at subatmospheric pressure. The findings reveal quantum tunneling rotors in metal-organic frameworks as a sensitive atomistic probe of local physicochemical phenomena.

We argue that the formation of Yu-Shiba-Rusinov excitations in proximitized thin films is largely mediated by a type of Andreev-bound state named after de Gennes and Saint-James. This is shown by studying an experimentally motivated model and computing the overlap of the wave functions of these two subgap states. We find the overlap stays close to unity even as the system moves away from weak coupling across the parity-changing quantum phase transition. Based on this observation, we introduce a single-site model of the bound state coupled to a quantum spin. The adequacy of this description is assessed by reintroducing the coupling to the continuum as a weak perturbation and studying its scaling flow using Anderson's poor man's scaling.

Dual scatterers preserve the helicity of an incident field, whereas antidual scatterers flip it completely. In this setting of linear electromagnetic scattering theory, we provide a completely general proof on the nonexistence of passive antidual scatterers. However, we show that scatterers fulfilling the refractive index matching condition flip the helicity of the fields very efficiently without being in contradiction with the law of energy conservation. Moreover, we find that this condition is paired with the impedance matching condition in several contexts of electromagnetism and, in particular, within Fresnel's and Mie's scattering problems. Finally, we show that index-matched media induce a resonant helicity mixing on the propagating electromagnetic waves. We reach this conclusion by identifying that the refractive index matching condition leads to the phenomenon of avoided crossing.

Yu-Shiba-Rusinov (YSR) states arise as subgap excitations of a magnetic impurity in a superconducting host. Taking into account the quantum nature of the impurity spin in a single-site approximation, we study the spectral properties of the YSR excitations of a system of magnetic impurity in a spin-split superconductor, i.e., a superconductor in proximity to a ferromagnetic insulator at zero external magnetic fields. The YSR excitations of this system exhibit a robust spin polarization that is protected from fluctuations and environmental noise by the exchange field of the ferromagnetic insulator, which can be as large as a few Tesla. We compare the results of this quantum approach to the classical approach, which conventionally predicts fully polarized YSR excitations even in the absence of exchange and external magnetic field. Turning on a small magnetic field, we show the latter splits the YSR excitations in the regime where the impurity is strongly coupled to the superconductor, whilst the classical approach predicts no such splitting. The studied system can potentially be realized in a tunnel junction connected to a quantum dot in proximity to a spin-split superconductor.

We investigate the behavior of magnetic impurities placed on the surface of superconductor thin films with spin-orbit coupling. Our study reveals long-range interactions between the impurities, which decay according to a power law, mediated by the interplay between the superfluid response described by the London equations and the anomalous supercurrents due to magnetoelectric effects. Importantly, these interactions possess a ferromagnetic component when considering the influence of the electromagnetic field, leading to the parallel alignment of the magnetic moments in the case of two impurities. In a Bravais lattice of magnetic impurities, superconductivity facilitates the establishment of ferromagnetic order within specific parameter ranges. These findings challenge the conventional understanding that ferromagnetism and superconductivity are mutually exclusive phenomena. Our theoretical framework provides a plausible explanation for the recently observed remanent flux and transport signature of ferromagnetism in iron-based superconductors, particularly Fe(Se,Te).

The precise structural details of metallic nanogaps within optical antennae are found to dramatically modify the plasmonic response, producing a complex pattern of electromagnetic modes that can be directly observed in scattering experiments. We analyze this situation theoretically in the nanoparticle-on-mirror construct, which forms a plasmonic nanogap sensitive to even atomic-scale restructuring of nanoparticle morphology. We focus on the effect of nanoparticle faceting, which allows the formation of ultrathin cavities between the particle and the underlying metallic film in the nanoparticle-on-mirror geometry. Two different sets of modes are identified: longitudinal antenna modes, which are strongly radiative and excited for all facet width ranges, and transverse cavity modes produced at large facets and exhibiting extreme confinement. The interaction and hybridization of antenna and cavity modes is determined by their symmetry and the precise morphology of the nanogap edges. Understanding such complex optics from nanoparticle-on-mirror structures is important to elucidate a wide variety of emerging photochemical and optoelectronic processes.

The polarization of the light scattered by an optically dense and random solution of dielectric nanoparticles shows peculiar properties when the scatterers exhibit strong electric and magnetic polarizabilities. While the distribution of the scattering intensity in these systems shows the typical irregular speckle patterns, the helicity of the incident light can be fully conserved when the electric and magnetic polarizabilities of the scatterers are equal. We show that the multiple scattering of helical beams by a random dispersion of >dual> dipolar nanospheres leads to a speckle pattern exhibiting a perfect isotropic constant polarization, a situation that could be useful in coherent control of light as well as in lasing in random media.

The molecular Schrödinger equation is rewritten in terms of nonunitary equations of motion for the nuclei (or electrons) that depend parametrically on the configuration of an ensemble of generally defined electronic (or nuclear) trajectories. This scheme is exact and does not rely on the tracing out of degrees of freedom. Hence, the use of trajectory-based statistical techniques can be exploited to circumvent the calculation of the computationally demanding Born-Oppenheimer potential-energy surfaces and nonadiabatic coupling elements. The concept of the potential-energy surface is restored by establishing a formal connection with the exact factorization of the full wave function. This connection is used to gain insight from a simplified form of the exact propagation scheme. © 2014 American Physical Society.

In this work we give a comprehensive derivation of an exact and numerically feasible method to perform ab-initio calculations of quantum particles interacting with a quantized electromagnetic field. We present a hierachy of density-functional-type theories that describe the interaction of charged particles with photons and introduce the appropriate Kohn-Sham schemes. We show how the evolution of a system described by quantum electrodynamics in Coulomb gauge is uniquely determined by its initial state and two reduced quantities. These two fundamental observables, the polarization of the Dirac field and the vector potential of the photon field, can be calculated by solving two coupled, non-linear evolution equations without the need to explicitly determine the (numerically infeasible) many-body wave function of the coupled quantum system. To find reliable approximations to the implicit functionals we present the according Kohn-Sham construction. In the non-relativistic limit this density-functional-type theory of quantum electrodynamics reduces to the density-functional reformulation of the Pauli-Fierz Hamiltonian, which is based on the current density of the electrons and the vector potential of the photon field. By making further approximations, e.g. restricting the allowed modes of the photon field, we derive further density functional-type theories of coupled matter-photon systems for the corresponding approximate Hamiltonians. In the limit of only two sites and one mode we deduce the according effective theory for the two-site Hubbard model coupled to one photonic mode. This model system is used to illustrate the basic ideas of a density-functional reformulation in great detail and we present the exact Kohn-Sham potentials for our coupled matter-photon model system.

The thermoelectric properties in one- and two-dimensional silicon and germanium structures have been investigated using first-principles density functional techniques and linear response for the thermal and electrical transport. We have considered here the two-dimensional silicene and germanene, together with nanoribbons of different widths. For the nano ribbons, we have also investigated the possibility of nano structuring these systems by mixing silicon and germanium. We found that the figure of merit at room temperature of these systems is remarkably high, up to 2.5.

One of the most accepted models that describe the anomalous thermal behavior of amorphous materials at temperatures below 1 K relies on the quantum mechanical tunneling of atoms between two nearly equivalent potential energy wells forming a two-level system (TLS). Indirect evidence for TLSs is widely available. However, the atomistic structure of these TLSs remains an unsolved topic in the physics of amorphous materials. Here, using classical molecular dynamics, we found several hitherto unknown bistable structural motifs that may be key to understanding the anomalous thermal properties of amorphous alumina at low temperatures. We show through free energy profiles that the complex potential energy surface can be reduced to canonical TLSs. The tunnel splitting predicted from instanton theory, the number density, dipole moment, and coupling to external strain of the discovered motifs are consistent with experiments.

The growth of the √3 × √3 reconstructed silicene on Ag substrate has been frequently observed in experiments while its atomic structure and formation mechanism is poorly understood. Here, by first-principles calculations, we show that √3 × √3 reconstructed silicene is constituted by dumbbell units of Si atoms arranged in a honeycomb pattern. Our model shows excellent agreement with the experimentally reported lattice constant and STM image. We propose a new mechanism for explaining the spontaneous and consequential formation of √3 × √3 structures from 3×3 structures on Ag substrate. We show that the √3 × √3 reconstruction is mainly determined by the interaction between Si atoms and have weak influence from Ag substrate. The proposed mechanism opens the path to understanding of multilayer silicon

The vibrational properties of ultrathin Bi(111) films have been calculated by applying density functional perturbation theory with and without the inclusion of spin-orbit interaction. Phonon dispersion curves of dynamically stable bilayers are presented and analyzed. Surprisingly, the Rayleigh mode is found to have the largest amplitude on the second atomic layer. Moreover an optical surface phonon branch is found to be localized above the optical band and confined within the first surface bilayer. The analysis of this mode as a function of the number of bilayers allows one to estimate the contribution of the spin-orbit coupling to the electron-phonon interactions. © 2013 American Physical Society.

Helium ion microscopy (HIM), which was released in 2006 by Ward et. al., provides non- destructive imaging of nano-scale objects with higher contrast than scanning electron microscopy. HIM measurement of suspended graphene under typical conditions was simulated by first-principles time-dependent density functional theory and the 30 keV He+ collision was found to induce the emission of electrons dependent on the impact point. This finding suggests possibility of obtaining a highly accurate image of the honeycomb pattern of suspended graphene by HIM. Comparison with a simulation of He0 under the same kinetic energy showed that electron emission is governed by the impact ionization instead of Auger process initiated by neutralization of He+.

We have used first-principles simulations based on time-dependent density functional theory to show that short laser pulses can trigger preferential hydrogen desorption from the upper or lower side of suspended graphane (H-terminated graphene). This control is achieved by using intense ultrashort p-polarized laser pulses (∼2 fs) with an asymmetric time envelope. The dynamical Stark effect induced by the pulse creates an asymmetric charge distribution and force field on the H ions, even at low laser fluence. At finite temperatures the carbon-hydrogen stretching softens, favoring H desorption from one side. This transient geometry can be modified by halogen functionalization, which results in a two-dimensional dipolar structure.

The study of two-dimensional (2D) electronic systems is of great fundamental significance in physics. Atomic layers containing hybridized domains of graphene and hexagonal boron nitride (h-BNC) constitute a new kind of disordered 2D electronic system. Magnetoelectric transport measurements performed at low temperature in vapor phase synthesized h-BNC atomic layers show a clear and anomalous transition from an insulating to a metallic behavior upon cooling. The observed insulator to metal transition can be modulated by electron and hole doping and by the application of an external magnetic field. These results supported by ab initio calculations suggest that this transition in h-BNC has distinctly different characteristics when compared to other 2D electron systems and is the result of the coexistence between two distinct mechanisms, namely, percolation through metallic graphene networks and hopping conduction between edge states on randomly distributed insulating h-BN domains. © 2012 American Physical Society.

The temperature dependence of the dynamics of electrons in the n=1 image potential state on the Ag(111) surface has been investigated by means of time-resolved two-photon photoemission spectroscopy and many-body calculations. We show that the decay rate of electrons in this state grows linearly with temperature. The thermal shortening of the lifetime is caused by the increase of the electron-electron scattering rate, due to deeper penetration of the image state wave function into the bulk metal at higher temperature. The electron-phonon scattering in this state is found to be small. © 2012 American Physical Society.

The dependence of the inelastic lifetime of electrons in the first n=1 image-potential state of clean and rare-gas covered Ag(111), Cu(111), and Cu(100) surfaces on their momentum parallel to the surface has been studied experimentally by means of time- and angle-resolved two-photon photoemission spectroscopy (2PPE) and theoretically by calculations based on the many-body theory within the self-energy formalism. Similar to the previously studied clean Cu(100) surface, the theoretical results are in excellent agreement with the experiment findings for Cu(111). For Ag(111), the theory overestimates the decay rate and its momentum dependence, which is attributed to the neglect of surface plasmon excitations. With increasing parallel momentum, the n=1 state shifts out of the projected bulk band gap on both surfaces and turns into an image-potential resonance. This opens an additional decay channel by resonant electron transfer into the bulk, which is theoretically treated by the application of the wave packet propagation approach. The expected stronger increase of the decay rate upon crossing the edge of the band gap, however, is not observed in the experiment. The decoupling of the image-potential states from the metal surface upon adsorption of rare-gas layers results in a decrease of the decay rate as well as of its momentum dependence by a similar factor, which can be successfully explained by the change of interband and intraband contributions to the total decay rate. © 2012 American Physical Society.

Spin-currents and non-Abelian gauge potentials in electronic systems can be treated by spin-current density-functional theory, whose main input is the exchange-correlation (xc) energy expressed as a functional of spin-currents. Constructing a functional of spin-currents that is invariant under U(1)×SU(2) transformations is a long-standing challenge. We solve the problem by expressing the energy as a functional of a variable we call “invariant vorticity.” As an illustration we construct the xc energy functional for a two-dimensional electron gas with linear spin-orbit coupling and show that it is proportional to the fourth power of the spin-current.

We derive a closed equation of motion for the current density of an inhomogeneous quantum many-body system under the assumption that the time-dependent wave function can be described as a geometric deformation of the ground-state wave function. By describing the many-body system in terms of a single collective field we provide an alternative to traditional approaches, which emphasize one-particle orbitals. We refer to our approach as continuum mechanics for quantum many-body systems. In the linear response regime, the equation of motion for the displacement field becomes a linear fourth-order integrodifferential equation, whose only inputs are the one-particle density matrix and the pair-correlation function of the ground state. The complexity of this equation remains essentially unchanged as the number of particles increases. We show that our equation of motion is a Hermitian eigenvalue problem, which admits a complete set of orthonormal eigenfunctions under a scalar product that involves the ground-state density. Further, we show that the excitation energies derived from this approach satisfy a sum rule which guarantees the exactness of the integrated spectral strength. Our formulation becomes exact for systems consisting of a single particle and for any many-body system in the high-frequency limit. The theory is illustrated by explicit calculations for simple one- and two-particle systems.

The recent work of Cavalieri et al. [Nature (London) 449, 1029 (2007)] has provided the first experimental observation of electron dynamics at metal surfaces in the subfemtosecond range. We explain the experimental findings using a full time-dependent approach within a one-dimensional model that includes the main ingredients of the short time physics involved in the experiment.

We develop the continuum mechanics of quantum many-body systems in the linear response regime. The basic variable of the theory is the displacement field, for which we derive a closed equation of motion under the assumption that the time-dependent wave function in a locally comoving reference frame can be described as a geometric deformation of the ground-state wave function. We show that this equation of motion is exact for systems consisting of a single particle, and for all systems at sufficiently high frequency, and that it leads to an excitation spectrum that has the correct integrated strength. The theory is illustrated by simple model applications to one- and two-electron systems.

Using the example of the Au(111) surface state, the hole inelastic lifetime in a two-dimensional electron system with spin-orbit interaction is investigated within the GW approximation. It is found that taking the spin-orbit interaction into account does not have a significant impact on the surface-state linewidth as a function of energy: for a given binding energy the two spin-orbit-split branches have nearly the same lifetimes. This trend is also observed in angle-resolved photoemission measurements. It is predicted that noticeable differences in the lifetimes of the split branches can be induced by tuning the strength of the splitting and the position of the Fermi level.

The coupling efficiency between an adsorbate and a two-dimensional substrate is probed by real-time monitoring of the ultrafast charge transfer between a Cs atom and an ultrathin silver film of varying thickness adsorbed on a Cu(111) surface. For the first two monolayers of the silver film, a reduction in the resonance lifetime of the cesium 6s−6p hybrid state of approximately 35% is observed. When the silver coverage further increases, the resonance lifetime stays constant at a value close to the value for Cs adsorption on a bulk Ag(111) surface. Both the one-electron resonant and the multielectron inelastic contributions to the adsorbate-substrate charge transfer are theoretically evaluated based on wave-packet propagation and GW approximation. The results support the experimental findings and allow us to assign the observed dependence of the lifetime change in the multielectron inelastic contribution to the electron transfer rate between the Cs resonance and the very top atomic layers of the substrate.

We present ab initio calculations of the electronic energy loss of charged particles moving outside a magnesium surface from a realistic description of the one-electron band structure and a full treatment of the dynamical electronic response of valence electrons. Our results indicate that the finite width of the plasmon resonance, which is mainly due to the presence of band-structure effects, strongly modifies the asymptotic behavior of the energy loss at large distances from the surface. This effect is relevant for the understanding of the interaction between charged particles and the internal surface of microcapillaries.

We report on the results of calculation of low-energy dielectric response and optical properties of MgB2. The calculations have been performed with full inclusion of the ab initio electron band structure making use of random-phase and time-dependent local-density approximations. The role of local-field and exchange-correlation effects in MgB2 dielectric function is thoroughly examined. Index of refraction, extinction coefficient, and normal-incidence reflectivity exhibiting strong anisotropy were calculated for electromagnetic waves polarized along the a∗ and c∗ axes by using the evaluated electron-density-response functions. Our results are in good agreement with recent x-ray and optical measurements performed on MgB2 single crystals.