Hybrid quantum-classical polarizability model for single molecule biosensing.

Optical whispering gallery mode biosensors are able to detect single molecules through effects of their polarizability. We address the factors that affect the polarizability of amino acids, which are the building blocks of life, via electronic structure theory. Amino acids are detected in aqueous environments, where their polarizability is different compared to the gasphase due to solvent effects. Solvent effects include structural changes, protonation and the local field enhancement through the solvent (water). We analyse the impact of these effects and find that all contribute to an increased effective polarizability in the solvent. We also address the excess polarizability relative to the displaced water cavity and develop a hybrid quantum-classical model that is in good agreement with self-consistent calculations. We apply our model to calculate the excess polarizability of 20 proteinogenic amino acids and determine the minimum resolution required to distinguish the different molecules and their ionised conformers based on their polarizability.

Origin of anomalously stabilizing ice layers on methane gas hydrates near rock surface.

Gas hydrates (GHs) in water close to freezing temperatures can be stabilised via the formation of ice layers. In a recent work [Boström et al., Astron. Astrophys., A54, 650, 2021], it was found that a surface region with partial gas dilution could be essential for obtaining nano- to micron-sized anomalously stabilizing ice layers. In this paper, it is demonstrated that the Casimir-Lifshitz free energy in multi-layer systems could induce thinner, but more stable, ice layers in cavities than those found for gas hydrates in a large reservoir of cold water. The thickness and stability of such ice layers in a pore filled with cold water could influence the leakage of gas molecules. Additional contributions, e.g. from salt-induced stresses, can also be of importance, and are briefly discussed.

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.

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.

Orientational Dependence of the van der Waals Interactions for Finite-Sized Particles.

Dispersion forces, especially van der Waals forces as interactions between neutral and polarizable particles act at small distances between two objects. Their theoretical origin lies in the electromagnetic interaction between induced dipole moments caused by the vacuum fluctuations of the ground-state electromagnetic field. The resulting theory well describes the experimental situation in the limit of the point dipole assumption. At smaller distances, where the finite size of the particles has to be taken into account, this description fails and has to be corrected by higher orders of the multipole expansion, such as quadrupole moments and so on. With respect to the complexity of the spatial properties of the particles this task requires a considerable effort. In order to describe the van der Waals interaction between such particles, we apply the established method of a spatially spread out polarizability distribution to approximate the higher orders of the multipole expansion. We thereby construct an effective theory for effects from anisotropy and finite size on the van der Waals potential.

Effective Polarizability Models.

Theories for the effective polarizability of a small particle in a medium are presented using different levels of approximation: we consider the virtual cavity, real cavity, and the hard-sphere models as well as a continuous interpolation of the latter two. We present the respective hard-sphere and cavity radii as obtained from density-functional simulations as well as the resulting effective polarizabilities at discrete Matsubara frequencies. This enables us to account for macroscopic media in van der Waals interactions between molecules in water and their Casimir-Polder interaction with an interface.