Eyringpy: A program for computing rate constants in the gas phase and in solution

Eyringpy is a modular program for calculating thermochemical properties and rate constants for reactions in the gas phase and in solution. The code is written in Python and it has a user-friendly interface and a simple input format. Unimolecular and bimolecular reactions with one and two products are supported. Thermochemical properties are estimated through canonical ensemble and rate constants are computed according to the transition state theory. One-dimensional Wigner and Eckart tunneling corrections are also available. Rate constants of bimolecular reactions involving the formation of pre-reactive complexes are also estimated. To compute rate constants in solution, Eyringpy uses the Collins–Kimball theory to include the diffusion-limit, the Marcus theory for electron transfer processes, and the molar fractions to account for the solvent pH effect.     

Structure and Bonding in CE5− (E=Al–Tl) Clusters: Planar Tetracoordinate Carbon versus Pentacoordinate Carbon

The structure, bonding, and stability of clusters with the empirical formula CE₅^? (E=Al–Tl) have been analyzed by means of high‐level computations. The results indicate that, whereas aluminum and gallium clusters have C_2v structures with a planar tetracoordinate carbon (ptC), their heavier homologues prefer three‐dimensional C_4v forms with a pentacoordinate carbon center over the ptC one. The reason for such a preference is a delicate balance between the interaction energy of the fifth E atom with CE₄ and the distortion energy. Moreover, bonding analysis shows that the ptC systems can be better described as CE₄^?, with 17‐valence electrons interacting with E. The ptC core in these systems exhibits double aromatic (both σ and π) behavior, but the σ contribution is dominating.     

How Many Water Molecules Does it Take to Dissociate HCl?

The potential energy surfaces of the HCl(H₂O)_n (n is the number of water molecules) clusters are systematically explored using density functional theory and high‐level ab initio computations. On the basis of electronic energies, the number of water molecules needed for HCl dissociation is four as reported by some experimental groups. However, this number is five owing to the inclusion of entropic factors. Wiberg bond indices are calculated and analyzed, and the results provide a quadratic correlation and classification of clusters according to the nondissociated, partially dissociated, and fully dissociated character of the H?Cl bond. Our computations show that if temperature is not controlled during the experiment, the values obtained for the dipole moment (or for any measurable property) are susceptible to change, providing a different picture of the number of water molecules needed for HCl dissociation in a nanoscopic droplet.     

Optical cloaking of cylindrical objects by using covers made of core-shell nanoparticles

In this Letter, we propose an engineered design of optical cloaks based on the scattering cancellation technique and intended to reduce the observability of cylindrical objects. The cover, consisting of a periodic arrangement of core-shell nanospheres, is designed in such a way to exhibit near-zero values of the real part of the homogenized effective permittivity at optical frequencies. Full-wave numerical simulations, considering the measured data of the dielectric function of the plasmonic material composing the shell, show that the cloak is able to reduce by about 6 dB the scattering cross section of a finite-length cylinder at around 740 THz with a -3 dB fractional bandwidth of about 7%. We show also that this result is not significantly affected by the perturbation of the periodic alignment of the core-shell nanospheres, due to possible fabrication issues or to an amorphous arrangement.     

Possible implementation of epsilon-near-zero metamaterials working at optical frequencies

Metamaterials (MTMs) exhibiting a near-zero real part of the permittivity function in a given frequency range have been demonstrated to be useful in several application fields, including field localization and focusing. So far, however, the realistic implementations of such materials working at optical frequencies and exhibiting a reasonable level of losses are rare. In this work, we propose a possible implementation of optical epsilon-near-zero (ENZ) MTMs based on the employment of an array of core-shell nano-spheres embedded in a dielectric medium. The core of the nano-spheres and the host medium are both made of silica, while the shell is formed by a plasmonic material (i.e. silver). Using classical homogenization formulas, we show that it is possible to design the array in such a way to exhibit near-zero values of the effective real permittivity with relatively low losses at optical frequencies. These results are supported and confirmed by proper full-wave simulations and design examples.     

Experimental demonstration of the enhanced transmission through circular and rectangular sub-wavelength apertures using omega-like split-ring resonators

Enhanced transmission through circular and rectangular sub-wavelength apertures using omega-shaped split-ring resonator is numerically and experimentally demonstrated at microwave frequencies. We report a more than 150,000-fold enhancement through a deep sub-wavelength aperture drilled in a metallic screen. To the authors’ best knowledge, this is the highest experimentally obtained enhancement factor reported in the literature. In the paper, we address also the origins and the physical reasons behind the enhancement results. Moreover, we report on the differences occurring when using circular, rectangular apertures as well as double-sided and single-sided omega-like split ring resonator structures.     

Cloaking apertureless near-field scanning optical microscopy tips

We numerically demonstrate that properly designed plasmonic covers can be used to enhance the performance of near-field scanning optical microscopy (NSOM) systems based on the employment of apertureless metallic tip probes. The covering material, exhibiting a near-zero value of the real permittivity at the working frequency, is designed in such a way to dramatically reduce the undesired scattering due to the strongly plasmonic behavior of the tip. Though the light scattering by the tip end is necessary for the correct operation of NSOMs, the additional scattering due to the whole probe affects the signal-to-noise ratio and thus the resolution of the acquired image. By covering the whole probe but not the very tip, we show that unwanted scattering can be effectively reduced. A realistic setup, working at mid-IR frequencies and employing silicon carbide covers, has been designed and simulated to confirm the effectiveness of the proposed approach.     

FSS-based approach for the power transmission enhancement through electrically small apertures

In this paper, a novel approach, based on the employment of frequency selective surfaces, to enhance the power transmission through sub-wavelength apertures at the microwave frequencies is presented. A heuristic interpretation of the phenomenon is given, as well as an analytical model, based on the transmission line network representation. Finally, the performance of the proposed structure is validated through a set of full-wave numerical simulations.     

SurfinPES: Performing automated analysis of activation strain,energy decomposition,and reaction force

Analyzing activation strain, energy decomposition, and reaction force models is crucial for studying chemical reactivity and gaining quantitative insights into the factors that control energy barriers. However, manually preparing and processing the necessary data can be challenging and prone to errors. To address this issue, we introduce SurfinPES, a Python-based module in Eyringpy that automates data extraction and processing for these analyses. SurfinPES also allows monitoring of the evolution of primitive properties (geometrical and electronic) along the reaction coordinate. The module is user-friendly with a simple input format, making it accessible to any user in the field of computational chemistry.     

Planar tetracoordinate fluorine atoms

Among the list of planar tetracoordinate atoms, fluorine is missing. So far, there are no theoretical or experimental reports suggesting their existence. Herein, we introduce the first six combinations (FIn₄⁺, FTl₄⁺, FGaIn₃⁺, FIn₂Tl₂⁺, FIn₃Tl⁺, and FInTl₃⁺) whose global minima contain a planar tetracoordinate fluorine. The bonding analyses indicate that the interactions between the fluorine and the peripheral atoms are significantly electrostatic, which is also reflected in the electronic delocalization. As opposed to other planar tetracoordinate systems with carbon, nitrogen, or oxygen atoms, the fluorine in the ptFs does not act as a σ-acceptor, restraining any back-donation. On the other hand, σ-electrons show a diatropic response, which would characterize these clusters as σ-aromatic.

The first global minima with a planar tetracoordinate fluorine atom are introduced. Their stabilization depends mainly on subtle ionic interactions and an adequate cavity.