Quantized Fields for Optimal Control in the Strong Coupling Regime.

We tailor the quantum statistics of a bosonic field to deterministically drive a quantum system into a target state. Experimentally accessible states of the field achieve good control of multilevel or multiqubit systems, notably also at coupling strengths beyond the rotating-wave approximation. This extends optimal control theory to the realm of fully quantized, strongly coupled control and target degrees of freedom.

Purcell-induced suppression of superradiance for molecular overlayers on noble atom surfaces.

We study the impact of an environment on the electromagnetic responses of a molecule in the presence of a dielectric medium. By applying the dipole-dipole coupling between the molecule's and the environment's degrees of freedom, we can reduce the complex system into its components and predict excitation lifetimes of single and few molecules attached to a dielectric surface by knowing the entire quantum-mechanical properties of the molecules, such as transition energies and dipole moments. The derived theory allows for the description of superradiance between two molecules depending on the geometric arrangement between both concerning their separation and orientation with respect to each other. We analyze the possibility of superradiance between two molecules bound to a dielectric sphere and determine a change in the relevant length scale where the usually considered wavelength in free space is replaced with the binding distance, drastically reducing the length scales at which collective effects can take place.

Detection of quantum-vacuum field correlations outside the light cone.

According to quantum field theory, empty space-the ground state with all real excitations removed-is not empty, but filled with quantum-vacuum fluctuations. Their presence can manifest itself through phenomena such as the Casimir force, spontaneous emission, or dispersion forces. These fluctuating fields possess correlations between space-time points outside the light cone, i.e. points causally disconnected according to special relativity. As a consequence, two initially uncorrelated quantum objects in empty space which are located in causally disconnected space-time regions, and therefore unable to exchange information, can become correlated. Here, we have experimentally demonstrated the existence of correlations of the vacuum fields for non-causally connected space-time points by using electro-optic sampling. This result is obtained by detecting vacuum-induced correlations between two 195 fs laser pulses separated by a time of flight of 470 fs. This work marks a first step in analyzing the space-time structure of vacuum correlations in quantum field theory.

Effective screening of medium-assisted van der Waals interactions between embedded particles.

The effect of an implicit medium on dispersive interactions of particle pairs is discussed, and simple expressions for the correction relative to vacuum are derived. We show that a single point Gauss quadrature leads to the intuitive result that the vacuum van der Waals C6-coefficient is screened by the permittivity squared of the environment evaluated near to the resonance frequencies of the interacting particles. This approximation should be particularly relevant if the medium is transparent at these frequencies. In this manuscript, we provide simple models and sets of parameters for commonly used solvents, atoms, and small molecules.

Macroscopic quantum electrodynamics and density functional theory approaches to dispersion interactions between fullerenes.

The processing and material properties of commercial organic semiconductors, for e.g. fullerenes is largely controlled by their precise arrangements, specially intermolecular symmetries, distances and orientations, more specifically, molecular polarisabilities. These supramolecular parameters heavily influence their electronic structure, thereby determining molecular photophysics and therefore dictating their usability as n-type semiconductors. In this article we evaluate van der Waals potentials of a fullerene dimer model system using two approaches: (a) Density Functional Theory and, (b) Macroscopic Quantum Electrodynamics, which is particularly suited for describing long-range van der Waals interactions. Essentially, we determine and explain the model symmetry, distance and rotational dependencies on binding energies and spectral changes. The resultant spectral tuning is compared using both methods showing correspondence within the constraints placed by the different model assumptions. We envision that the application of macroscopic methods and structure/property relationships laid forward in this article will find use in fundamental supramolecular electronics.

Signature of Short-Range van der Waals Forces Observed in Poisson Spot Diffraction with Indium Atoms.

The phase of de Broglie matter waves is a sensitive probe for small forces. In particular, the attractive van der Waals force experienced by polarizable atoms in the close vicinity of neutral surfaces is of importance in nanoscale systems. It results in a phase shift that can be observed in matter-wave diffraction experiments. Here, we observe Poisson spot diffraction of indium atoms at submillimeter distances behind spherical submicron silicon dioxide particles to probe the dispersion forces between atoms and the particle surfaces. We compare the measured relative intensity of Poisson's spot to theoretical results derived from first principles in an earlier communication and find a clear signature of the atom-surface interaction.

Premelting of ice adsorbed on a rock surface.

Considering ice-premelting on a quartz rock surface (i.e. silica) we calculate the Lifshitz excess pressures in a four layer system with rock-ice-water-air. Our calculations give excess pressures across (1) ice layer, (2) water layer, and (3) ice-water interface for different ice and water layer thicknesses. We analyse equilibrium conditions where the different excess pressures take zero value, stabilized in part by repulsive Lifshitz interactions. In contrast to previous investigations which considered varying thickness of only one layer (ice or water), here we present theory allowing for simultaneous variation of both layer thicknesses. For a given total thickness of ice and water, this allows multiple alternative equilibrium solutions. Consequently the final state of a system will depend on initial conditions and may explain variation in experimental measurements of the thicknesses of water and ice layers.

Full-Spectrum High-Resolution Modeling of the Dielectric Function of Water.

In view of the vital role of water, exact knowledge of its dielectric function over a large frequency range is important. We report on currently available measurements of the dielectric function of water at room temperature (25 °C) across the full spectrum: microwave, IR, UV, and X-ray (up to 100 eV). We parameterize the complex dielectric function of water with two Debye (microwave) oscillators and high resolution of IR and UV/X-ray oscillators. We also report dielectric parameters for ice-cold water with a microwave/IR spectrum measured at 0.4 °C, while taking the UV spectrum at 25 °C (assuming negligible temperature dependence in UV). We employ van der Waals dispersion interactions to contrast our model of ice-cold water with earlier models. Air bubbles in water and dissolved gas molecules show attraction toward interfaces rather than repulsion. The van der Waals interaction promotes complete freezing rather than supporting a thin layer of water on ice. We infer that premelting is driven by charge and ion adsorption. Density-based extrapolation from warm to cold water of the dielectric function is satisfactory in microwave but poor (40% error) at IR frequencies.

Impact of effective polarisability models on the near-field interaction of dissolved greenhouse gases at ice and air interfaces.

We present a theory for Casimir-Polder forces acting on greenhouse gas molecules dissolved in a thin water film. Such a nano-sized film has been predicted to arise on the surface of melting ice as stabilized by repulsive Lifshitz forces. We show that different models for the effective polarisability of greenhouse gas molecules in water lead to different predictions for how Casimir-Polder forces influence their extractions from the melting ice surface. For instance, in the most intricate model of a finite-sized molecule inside a cavity, dispersion potentials push the methane molecules towards the ice surface whereas the oxygen typically will be attracted towards the closest interface (ice or air). Previous models for effective polarisability had suggested that O2 would also be pushed towards the ice surface. Release of greenhouse gas molecules from the surface of melting ice can potentially influence climate greenhouse effects. With this model, we show that some molecules cannot escape from water as single molecules. Due to the contradiction of the results and the escape dynamics of gases from water, we extended the models to describe bubble filled with several molecules increasing their buoyancy force.

Virtual Photon Approximation for Three-Body Interatomic Coulombic Decay.

Interatomic Coulombic decay (ICD) is a mechanism that allows microscopic objects to rapidly exchange energy. When the two objects are distant, the energy transfer between the donor and acceptor species takes place via the exchange of a virtual photon. On the contrary, recent ab initio calculations have revealed that the presence of a third passive species can significantly enhance the ICD rate at short distances due to the effects of electronic wave function overlap and charge transfer states [Phys. Rev. Lett. 119, 083403 (2017)PRLTAO0031-900710.1103/PhysRevLett.119.083403]. Here, we develop a virtual photon description of three-body ICD, allowing us to investigate retardation and geometrical effects which are out of reach for current ab initio techniques. We show that a passive atom can have a significant influence on the rate of the ICD process at fairly large interatomic distances, due to the scattering of virtual photons off the mediator. Moreover, we demonstrate that in the retarded regime ICD can be substantially enhanced or suppressed depending on the position of the ICD-inactive object, even if the latter is far from both donor and acceptor species.

Nonadditivity of Optical and Casimir-Polder Potentials.

An atom irradiated by an off-resonant laser field near a surface is expected to experience the sum of two fundamental potentials, the optical potential of the laser field and the Casimir-Polder potential of the surface. Here, we report a new nonadditive potential, namely, the laser-induced Casimir-Polder potential, which arises from a correlated coupling of the atom with both the laser and the quantum vacuum. We apply this result to an experimentally realizable scenario of an atomic mirror with an evanescent laser beam leaking out of a surface. We show that the nonadditive term is significant for realistic experimental parameters, transforming potential barriers into potential wells, which can be used to trap atoms near surfaces.

The influence of retardation and dielectric environments on interatomic Coulombic decay.

Interatomic Coulombic decay (ICD) is a very efficient process by which high-energy radiation is redistributed between molecular systems, often producing a slow electron, which can be damaging to biological tissue. During ICD, an initially-ionised and highly-excited donor species undergoes a transition where an outer-valence electron moves to a lower-lying vacancy, transmitting a photon with sufficient energy to ionise an acceptor species placed close by. Traditionally the ICD process has been described via ab initio quantum chemistry based on electrostatics in free space, which cannot include the effects of retardation stemming from the finite speed of light, nor the influence of a dispersive, absorbing, discontinuous environment. Here we develop a theoretical description of ICD based on macroscopic quantum electrodynamics in dielectrics, which fully incorporates all these effects, enabling the established power and broad applicability of macroscopic quantum electrodynamics to be unleashed across the fast-developing field of ICD.

Strong van der Waals Adhesion of a Polymer Film on Rough Substrates.

We propose that chemically inert polymeric films can enhance van der Waals (vdW) forces in the same way as nanofabrication of biomimetic adhesive materials. For the vdW adhesion of an ethylene-chlorotrifluoroethylene (ECTFE) film on rough metal and dielectric substrates, we present a model that combines microscopic quantum-chemistry simulations of the polymer response functions and the equilibrium monomer-substrate distance with a macroscopic quantum-electrodynamics calculation of the Casimir force between the polymer film and the substrate. We predict adhesive forces up to 2.22 kN/mm2, where the effect is reduced by substrate roughness and for dielectric surfaces.

Enhanced Chiral Discriminatory van der Waals Interactions Mediated by Chiral Surfaces.

We predict a discriminatory interaction between a chiral molecule and an achiral molecule which is mediated by a chiral body. To achieve this, we generalize the van der Waals interaction potential between two ground-state molecules with electric, magnetic, and chiral response to nontrivial environments. The force is evaluated using second-order perturbation theory with an effective Hamiltonian. Chiral media enhance or reduce the free interaction via many-body interactions, making it possible to measure the chiral contributions to the van der Waals force with current technology. The van der Waals interaction is discriminatory with respect to enantiomers of different handedness and could be used to separate enantiomers. We also suggest a specific geometric configuration where the electric contribution to the van der Waals interaction is zero, making the chiral component the dominant effect.

Friction forces on atoms after acceleration.

The aim of this paper is to revisit the calculation of atom-surface quantum friction in the quantum field theory formulation put forward by Barton (2010 New J. Phys. 12 113045). We show that the power dissipated into field excitations and the associated friction force depend on how the atom is boosted from being initially at rest to a configuration in which it is moving at constant velocity (v) parallel to the planar interface. In addition, we point out that there is a subtle cancellation between the one-photon and part of the two-photon dissipating power, resulting in a leading order contribution to the frictional power which goes as v(4). These results are also confirmed by an alternative calculation of the average radiation force, which scales as v(3).

Temperature-independent Casimir-Polder forces despite large thermal photon numbers.

We demonstrate that Casimir-Polder potentials can be entirely independent of temperature even when allowing for the relevant thermal photon numbers to become large. This statement holds for potentials that are due to low-energy transitions of a molecule placed near a plane metal surface whose plasma frequency is much larger than any atomic resonance frequencies. For a molecule in an energy eigenstate, the temperature independence is a consequence of strong cancellations between nonresonant potential components and those due to evanescent waves. For a molecule with a single dominant transition in a thermal state, upward and downward transitions combine to form a temperature-independent potential. The results are contrasted with the case of an atom whose potential exhibits a regime of linear temperature dependence. Contact with the Casimir force between a weakly dielectric and a metallic plate is made.

Universal scaling laws for dispersion interactions.

We study the scaling behavior of dispersion potentials and forces under very general conditions. We prove that a rescaling of an arbitrary geometric arrangement by a factor a changes the atom-atom and atom-body potentials in the long-distance limit by factors 1/a{7} and 1/a{4}, respectively, and the Casimir force per unit area by 1/a{4}. In the short-distance regime, electric and magnetic bodies lead to different scaling behavior. As applications, we present scaling functions for two atom-body potentials and display the equipotential lines of a plate-assisted two-atom potential.

Macroscopic quantum electrodynamics and duality.

We discuss under what conditions the duality between electric and magnetic fields is a valid symmetry of macroscopic quantum electrodynamics. It is shown that Maxwell's equations in the absence of free charges satisfy duality invariance on an operator level, whereas this is not true for Lorentz forces and atom-field couplings in general. We prove that derived quantities such as Casimir forces, local-field corrected decay rates, as well as van der Waals potentials are invariant with respect to a global exchange of electric and magnetic quantities. This exact symmetry can be used to deduce the physics of new configurations on the basis of already established ones.

Thermal Casimir versus Casimir-Polder forces: equilibrium and nonequilibrium forces.

We critically discuss whether and under what conditions Lifshitz theory may be used to describe thermal Casimir-Polder forces on atoms or molecules. An exact treatment of the atom-field coupling reveals that for a ground-state atom (molecule), terms associated with virtual-photon absorption lead to a deviation from the traditional Lifshitz result; they are identified as a signature of nonequilibrium dynamics. Even the equilibrium force on a thermalized atom (molecule) may be overestimated when using the ground-state polarizability instead of its thermal counterpart.