Karlsenrichter7768

It is shown that the SO-SCI optimization provides faster and more robust convergence than the standard SCF procedure but requires, in many cases, even less computation time. In difficult cases, the SO-SCI method not only speeds up convergence but also avoids convergence to saddle-points. Furthermore, it helps to find spin-symmetry broken solutions in the cases of UHF or UKS. In the case of CAHF, convergence can also be significantly improved as compared to a previous SCF implementation. This is particularly important for multi-center cases with two or more equal heavy atoms. The performance is demonstrated for various two-center complexes with different lanthanide atoms.We model a binary mixture of passive and active Brownian particles in two dimensions using the effective interaction between passive particles in the active bath. The activity of active particles and the size ratio of two types of particles are the two control parameters in the system. The effective interaction is calculated from the average force on two particles generated by the active particles. The effective interaction can be attractive or repulsive, depending on the system parameters. The passive particles form four distinct structural orders for different system parameters, viz., homogeneous structures, disordered cluster, ordered cluster, and crystalline structure. The change in structure is dictated by the change in nature of the effective interaction. We further confirm the four structures using a full microscopic simulation of active and passive mixture. Our study is useful to understand the different collective behavior in non-equilibrium systems.Despite great efforts over the past 50 years, the simulation of water still presents significant challenges and open questions. At room temperature and pressure, the collective molecular interactions and dynamics of water molecules may form local structural arrangements that are non-trivial to classify. Here, we employ a data-driven approach built on Smooth Overlap of Atomic Position (SOAP) that allows us to compare and classify how widely used classical models represent liquid water. Macroscopically, the obtained results are rationalized based on water thermodynamic observables. Microscopically, we directly observe how transient ice-like ordered environments may dynamically/statistically form in liquid water, even above freezing temperature, by comparing the SOAP spectra for different ice structures with those of the simulated liquid systems. This confirms recent ab initio-based calculations but also reveals how the emergence of ephemeral local ice-like environments in liquid water at room conditions can be captured by classical water models.Transition metal dichalcogenides (TMDs) are regarded as a possible material platform for quantum information science and related device applications. In TMD monolayers, the dephasing time and inhomogeneity are crucial parameters for any quantum information application. In TMD heterostructures, coupling strength and interlayer exciton lifetimes are also parameters of interest. However, many demonstrations in TMDs can only be realized at specific spots on the sample, presenting a challenge to the scalability of these applications. Here, using multi-dimensional coherent imaging spectroscopy, we shed light on the underlying physics-including dephasing, inhomogeneity, and strain-for a MoSe2 monolayer and identify both promising and unfavorable areas for quantum information applications. We, furthermore, apply the same technique to a MoSe2/WSe2 heterostructure. Despite the notable presence of strain and dielectric environment changes, coherent and incoherent coupling and interlayer exciton lifetimes are mostly robust across the sample. This uniformity is despite a significantly inhomogeneous interlayer exciton photoluminescence distribution that suggests a bad sample for device applications. This robustness strengthens the case for TMDs as a next-generation material platform in quantum information science and beyond.Employing classical isothermal molecular dynamics, we simulated coalescence of mesoscopic Au nanodroplets, containing from several thousands to several hundred thousands of atoms, and sintering of mesoscopic solid Au nanoparticles. For our atomistic simulations, we used the embedded atom method. The employed open access program large-scale atomic/molecular massively parallel simulator makes it possible to realize parallel graphical processing unit calculations. We have made a conclusion that the regularities and mechanisms of the nanodroplet coalescence (temperature is higher than the nanoparticle melting temperature) and of the solid nanoparticle sintering differ from each other. We have also concluded that the nanodroplet coalescence may be interpreted as a hydrodynamic phenomenon at the nanoscale whereas sintering of solid nanoparticles is a much more complex phenomenon related to different mechanisms, including collective rearrangements of atoms, the surface diffusion, and other types of diffusion. At the same time, collective rearrangements of atoms relate not only to the solid nanoparticle sintering but also to the nanodroplet coalescence. In general, our molecular dynamics results on sintering of Au nanoparticles consisting of 10 000-30 000 atoms agree with the Ferrando-Minnai kinetic trapping concept that was earlier confirmed in molecular dynamics experiments on Au nanoclusters consisting of about 100 atoms.Cellulose nanocrystals (CNCs) are rodlike biosourced colloidal particles used as key building blocks in a growing number of materials with innovative mechanical or optical properties. While CNCs form stable suspensions at low volume fractions in pure water, they aggregate in the presence of salt and form colloidal gels with time-dependent properties. Here, we study the impact of salt concentration on the slow aging dynamics of CNC gels following the cessation of a high-shear flow that fully fluidizes the sample. We show that the higher the salt content, the faster the recovery of elasticity upon flow cessation. Most remarkably, the elastic modulus G' obeys a time-composition superposition principle the temporal evolution of G' can be rescaled onto a universal sigmoidal master curve spanning 13 orders of magnitude in time for a wide range of salt concentrations. Such a rescaling is obtained through a time-shift factor that follows a steep power-law decay with increasing salt concentration until it saturates at large salt content. These findings are robust to changes in the type of salt and the CNC content. We further show that both linear and nonlinear rheological properties of CNC gels of various compositions, including, e.g., the frequency-dependence of viscoelastic spectra and the yield strain, can be rescaled based on the sample age along the general master curve. Our results provide strong evidence for universality in the aging dynamics of CNC gels and call for microstructural investigations during recovery as well as theoretical modeling of time-composition superposition in rodlike colloids.Responsive polyzwitterionic materials have become important for a range of applications such as environmental remediation and targeted drug delivery. Much is known about the macroscopic phase-behaviors of such materials, but how the smaller scale single-chain structures of polyzwitterions respond to external stimuli is not well understood, especially at temperatures close to their phase boundaries. Such chain conformation responses are important in directing larger-scale associative properties. Here, we study the temperature dependent single-chain structure of a model polysulfobetaine, poly[3-(acrylamidopropyl-dimethyl-ammonium) propyl-1-sulfonate], using small angle neutron scattering. In the absence of salt, we find that temperature has a large effect on solvent quality with a decreasing trend from good solvent conditions at 50 °C to poor solvent at 10 °C (a temperature just above the cloud point of 7.6 °C) and an estimated theta temperature of 39 °C. When 100 mM NaCl is present, the solvent quality is good with weak temperature dependence. Without salt present, the polymer chain appears to have a nearly Gaussian coil conformation and the backbone becomes slightly more rigid as the temperature is lowered to the cloud point as determined by the Debye-local rod model on a Kratky plot. The addition of salt has a notable effect on the intra-chain correlations where an increase in chain dimensions to a swollen coil conformation and an increase in chain rigidity is observed at 100 mM NaCl in D2O, however, with a negligible temperature dependence.Time-dependent density functional theory (TDDFT) based approaches have been developed in recent years to model the excited-state properties and transition processes of the molecules in the gas-phase and in a condensed medium, such as in a solution and protein microenvironment or near semiconductor and metal surfaces. In the latter case, usually, classical embedding models have been adopted to account for the molecular environmental effects, leading to the multi-scale approaches of TDDFT/polarizable continuum model (PCM) and TDDFT/molecular mechanics (MM), where a molecular system of interest is designated as the quantum mechanical region and treated with TDDFT, while the environment is usually described using either a PCM or (non-polarizable or polarizable) MM force fields. In this Perspective, we briefly review these TDDFT-related multi-scale models with a specific emphasis on the implementation of analytical energy derivatives, such as the energy gradient and Hessian, the nonadiabatic coupling, the spin-orbit coupling, and the transition dipole moment as well as their nuclear derivatives for various radiative and radiativeless transition processes among electronic states. Three variations of the TDDFT method, the Tamm-Dancoff approximation to TDDFT, spin-flip DFT, and spin-adiabatic TDDFT, are discussed. Moreover, using a model system (pyridine-Ag20 complex), we emphasize that caution is needed to properly account for system-environment interactions within the TDDFT/MM models. Specifically, one should appropriately damp the electrostatic embedding potential from MM atoms and carefully tune the van der Waals interaction potential between the system and the environment. We also highlight the lack of proper treatment of charge transfer between the quantum mechanics and MM regions as well as the need for accelerated TDDFT modelings and interpretability, which calls for new method developments.Understanding how electrolyte-filled porous electrodes respond to an applied potential is important to many electrochemical technologies. Here, we consider a model supercapacitor of two blocking cylindrical pores on either side of a cylindrical electrolyte reservoir. A stepwise potential difference 2Φ between the pores drives ionic fluxes in the setup, which we study through the modified Poisson-Nernst-Planck equations, solved with finite elements. read more We focus our discussion on the dominant timescales with which the pores charge and how these timescales depend on three dimensionless numbers. Next to the dimensionless applied potential Φ, we consider the ratio R/Rb of the pore's resistance R to the bulk reservoir resistance Rb and the ratio rp/λ of the pore radius rp to the Debye length λ. We compare our data to theoretical predictions by Aslyamov and Janssen (Φ), Posey and Morozumi (R/Rb), and Henrique, Zuk, and Gupta (rp/λ). Through our numerical approach, we delineate the validity of these theories and the assumptions on which they were based.