Enhanced third harmonic generation in periodic structures

We consider third harmonic generation in a periodic layered medium with alternate nonlinear media. We show enhanced third harmonic generation when the fundamental frequency matches one of the mode frequencies of the distributed feedback structure. The observed feature is explained in terms of large local field enhancement for the fundamental wave.     

Bromine-bromine energy transfer by binary collisions

The collisional energy transfer between a highly excited bromine molecule and a non-reactive monatomic (Ar or Br) or diatomic (Br₂) medium has been investigated by binary trajectory calculations over a wide range of medium temperatures and internal energies of the reactant molecule. The efficiency of the energy transfer is compared with expectations based on simple statistical approximations used in unimolecular reaction rate theory. Large deviations are found, particularly with respect to the contributions made by different types of degrees of freedom and to the dependence on the internal energy of the reactant molecule. Transfer to or from vibrational degrees of freedom appears to be very inefficient. Translational energy is most readily transferred. The rate coefficient for energy transfer appears to decrease with increasing internal energy in most cases.     

New infrared integrated band intensities for HC3N and extensive line list for the ν5 and ν6 bending modes

The infrared spectrum of cyanoacetylene (also called propynenitrile) has been investigated from 400 to 4000 cm⁻¹ at a resolution of 0.5 cm⁻¹. Integrated intensities of the main bands and a number of weaker bands have been obtained with an uncertainty better than 5%. Inaccurate values in previous studies have been identified in particular concerning the intensity of the strong ν₅ stretching band at 663.2 cm⁻¹. Former results on the temperature dependence of integrated intensities have also been revisited.Synthetic spectra calculation has been performed for the ν₅ and ν₆ bands on the basis of the best available high resolution data. It has been shown that the GEISA line parameters for HC₃N are not sufficient to reproduce the band intensities and some hot band features observed in our experimental spectra at room temperature. As a first step, the model spectra has been improved by including a number of missing hot subbands and by calculating accurately the hot band relative intensities. Finally, a perfect agreement between calculated and observed spectra was achieved on the basis of a global analysis of HC₃N levels up to 2000 cm⁻¹ combined with the new integrated intensity measurements. A new extensive line list for the ν₅ and ν₆ bending modes of HC₃N has been compiled.     

Long-Term Stability Analysis of 3D and 2D/3D Hybrid Perovskite Solar Cells Using Electrochemical Impedance Spectroscopy

Despite the remarkable progress in perovskite solar cells (PSCs), their instability and rapid degradation over time still restrict their commercialization. A 2D capping layer has been proved to overcome the stability issues; however, an in-depth understanding of the complex degradation processes over a prolonged time at PSC interfaces is crucial for improving their stability. In the current work, we investigated the stability of a triple cation 3D ([(FA_0.83MA_0.17)Cs_0.05]Pb(I_0.83Br_0.17)₃) and 2D/3D PSC fabricated by a layer-by-layer deposition technique (PEAI-based 2D layer over triple cation 3D perovskite) using a state-of-art characterization technique: electrochemical impedance spectroscopy (EIS). A long-term stability test over 24 months was performed on the 3D and 2D/3D PSCs with an initial PCE of 18.87% and 20.21%, respectively, to suggest a more practical scenario. The current-voltage (J-V) and EIS results showed degradation in both the solar cell types; however, a slower degradation rate was observed in 2D/3D PSCs. Finally, the quantitative analysis of the key EIS parameters affected by the degradation in 3D and 2D/3D PSCs were discussed.     

High-resolution mining of the SARS-CoV-2 main protease conformational space: supercomputer-driven unsupervised adaptive sampling

We provide an unsupervised adaptive sampling strategy capable of producing μs-timescale molecular dynamics (MD) simulations of large biosystems using many-body polarizable force fields (PFFs). The global exploration problem is decomposed into a set of separate MD trajectories that can be restarted within a selective process to achieve sufficient phase-space sampling. Accurate statistical properties can be obtained through reweighting. Within this highly parallel setup, the Tinker-HP package can be powered by an arbitrary large number of GPUs on supercomputers, reducing exploration time from years to days. This approach is used to tackle the urgent modeling problem of the SARS-CoV-2 Main Protease (M^pro) producing more than 38 μs of all-atom simulations of its apo (ligand-free) dimer using the high-resolution AMOEBA PFF. The first 15.14 μs simulation (physiological pH) is compared to available non-PFF long-timescale simulation data. A detailed clustering analysis exhibits striking differences between FFs, with AMOEBA showing a richer conformational space. Focusing on key structural markers related to the oxyanion hole stability, we observe an asymmetry between protomers. One of them appears less structured resembling the experimentally inactive monomer for which a 6 μs simulation was performed as a basis for comparison. Results highlight the plasticity of the M^pro active site. The C-terminal end of its less structured protomer is shown to oscillate between several states, being able to interact with the other protomer, potentially modulating its activity. Active and distal site volumes are found to be larger in the most active protomer within our AMOEBA simulations compared to non-PFFs as additional cryptic pockets are uncovered. A second 17 μs AMOEBA simulation is performed with protonated His172 residues mimicking lower pH. Data show the protonation impact on the destructuring of the oxyanion loop. We finally analyze the solvation patterns around key histidine residues. The confined AMOEBA polarizable water molecules are able to explore a wide range of dipole moments, going beyond bulk values, leading to a water molecule count consistent with experimental data. Results suggest that the use of PFFs could be critical in drug discovery to accurately model the complexity of the molecular interactions structuring M^pro.

We provide an unsupervised adaptive sampling strategy capable of producing μs-timescale molecular dynamics (MD) simulations of large biosystems using many-body polarizable force fields (PFFs).     

Efficient Sorption of Basic Organic Dyes from Aqueous Solution Using Green Synthesized Silver Nanoparticles Beads

In this article, the potential of alginate stabilized silver nanoparticles beads for efficient sorption of methylene blue, malachite green, and rhodamine B from aqueous solutions was investigated. The adsorption data have been correlated with both Freundlich and Langmuir adsorption models. The kinetic studies for dyes adsorption showed rapid sorption dynamics by second-order kinetic model. The common problem of classical adsorbents towards efficient recyclability was overcome when alginate stabilized silver nanoparticles beads was used. The alginate stabilized silver nanoparticles beads were successfully recycled for 25 successive adsorption-desorption cycles indicating its high reusability.     

Linear periodic and quasiperiodic anisotropic layered media with arbitrary orientation of optic axis—A numerical study

We study numerically the linear properties of periodic and quasiperiodic anisotropic layered media. Each anisotropic slab can have arbitrary orientation of optic axis. We apply the general numerical code to recover the known results for solc filters. We propose novel periodic structures where the location and width of the gaps can be controlled easily. We also study the transmission properties of a Fibonacci sequence of anisotropic layers and show the interesting features like self-similarity and scaling.