Glassy dynamics of model colloidal polymers: Effect of controlled chain stiffness

Colloidal polymers with tunable chain stiffness have been successfully assembled in experiments recently.Similar to molecular polymers,chain stiffness is an important feature which can distinctly affect the dynamical behaviors of colloidal polymers.Hence,we model colloidal polymers with controlled chain stiffness and study the effect of chain stiffness on glassy behaviors.For stiff chains,there are long-ranged periodic intrachain correlations besides two incompatible local length scales,i.e.,monomer size and bond length.The mean square displacement of monomers exhibits sub-diffusion at intermediate time/length scale and the sub-diffusive exponent increases with chain stiffness.The data of localization length of stiff polymers versus rescaled volume fraction for different monomer sizes can gather close to an exponential curve and decay slower than those of flexible polymers.The increase of chain stiffness linearly increases the activation energy of the colloidal-polymer system and thus makes the colloidal polymers vitrify at lower volume fraction.Static and dynamic equivalences between stiff colloidal polymers of different monomer sizes have been checked.

Confined subdiffusion in three dimensions

Three-dimensional （3D） Fick＇s diffusion equation and fractional diffusion equation are solved for different reflecting boundaries. We use the continuous time random walk model （CTRW） to investigate the time-averaged mean square dis- placement （MSD） of a 3D single particle trajectory. Theoretical results show that the ensemble average of the time-averaged MSD can be expressed analytically by a Mittag-Leffler function. Our new expression is in agreement with previous formu- las in two limiting cases： （^-δ2） ~ △1 in short lag time and （^-δ2} ~ △1 -α in long lag time. We also simulate the experimental data of mRNA diffusion in living E. coli using a 3D CTRW model under confined and crowded conditions. The simulation results are well consistent with experimental results. The calculations of power spectral density （PSD） further indicate the subdiffsive behavior of an individual trajectory.

Experimental and computational analysis of the structure-activity relationship of ionic gel electrolytes based on bistrifluoromethanesulfonimide salts for supercapacitors

Ionic gel(IG)electrolytes are emerging as promising components for the development of next-generation supercapacitors(SCs),offering benefits in terms of safety,cost-effectiveness,and flexibility.The ionic conductivity,stability,and mechanical properties of the gel electrolyte are relevant factors to be considered and the key to improving the performance of the SC.However,the structure–activity relationship between the internal structure of IGs and their SC properties is not fully understood.In the current study,the intuitive and regular structure–activity relationship between the structure and properties of IGs was revealed via combining computational simulation and experiment.In terms of conductivity,the ionic liquid(IL)([EMIM][TFSI])in the IG has a high self-diffusion coefficient calculated by molecular dynamics simulation(MDS),which is conductive to transfer and then improves the conductivity.The radial distribution function of the MDS shows that the larger the g(r)between the particles in the polymer network,the stronger the interaction.For stability,IGs based on[EMIM][TFSI]and[EOMIM][TFSI]ILs have higher density functional theory calculated binding energy,which is reflected in the excellent thermal stability and excellent capacitor cycle stability.Based on the internal pore size distribution and stress-strain characterization of the gel network([ME3MePy][TFSI]and[BMIM][TFSI]as additives),the highly crosslinked aggregate network significantly reduces the internal mesoporous distribution and plays a leading role in improving the mechanical properties of the network.By using this strategy,it will be possible to design the ideal structure of the IG and achieve excellent performance.

Error Inhomogeneity in the Computation of Spherical Mean Displacement

The traditional method for computing the mean displacement in latitude-longitude coordinates is a spherical meridional-zonal resultant displacement method （MRDM）, which regards the displacement as the resultant vector of the meridional and zonal displacement components. However, there are inhomogeneity and singularity in the computation error of the MRDM, especially at high latitudes. Using the NCEP/NCAR long-term monthly mean wind and idealized wind fields, the inhomogeneity in the MRDM was accessed by using a great circle displacement computing method （GCDM） for non-iterative cases. The MRDM and GCDM were also compared for iteration cases by taking the trajectories from a three-time level reference method as the real trajectories. In the horizontal direction, the GCDM assumes that an air particle moves along its locating great circle and that the magnitude of the displacement equals the arc length of the great circle. The inhomogeneity of the MRDM is evaluated in terms of the horizontal dis- tance error from the products of wind speed, lapse time, and angle difference from the GCDM displacement orient. The non-iterative results show that the mean horizontal displacement computed through the MRDM has both compu- tational and analytical errors. The displacement error of the MRDM depends on the wind speed, wind direction, and the departure latitude of the air particle. It increases with the wind speed and the departure latitude. The displacement magnitude error has a four-wave pattern and the displacement direction error has a two-wave feature in the definition range of the wind direction. The iterative result shows that the displacement magnitude error and angle error of the MRDM and GCDM with respect to the reference method increase with the lapse time and have similar distribution patterns. The mean magnitude error and the angle error of the MRDM are nearly twice as large as those of the GCDM.

Molecular Dynamics Simulation of Diffusion of Vitamin C in Water Solution

Under different temperatures and concentrations, the diffusion of Vitamin C （VC） in water solution was exam- ined by molecular dynamics simulation. The diffusion coefficients were calculated based on the Einstein equation. The influences of temperature, concentration, and simulation time on the diffusion coefficient were discussed. The results showed that at higher temperature and lower concentration the normal diffusions appear relatively late, but the linear range of mean square displacement curves continues longer than that at lower temperature and higher concentration. At the same temperature, the normal diffusion time increases and the diffusion coefficient decreases as the simulation concentration increases. These simulation results are in good agreement with experiments. Analyses of the pair correlation functions of the simulation systems showed that hydrogen bonds are mainly formed be- tween the hydrogen atoms of VC molecules and oxygen atoms of H20 molecules, rather than between the O atoms of VC molecules and H atoms of H20 molecules. The diffusion coefficient is higher as the interaction between water molecules and VC molecules is stronger when VC concentration is lower. The water in the model systems affects the diffusion of VC molecules by the short-range repulsion of O（H20）-O（H20） pairs and the non-bond interaction of H（H20）-H（H20） pairs. The short-range repulsion of O（H20）-O（H20） pairs is greater when VC concentration is higher, the diffusion of VC is weaker. The greater the non-bond interaction of H（H20）-H（H20） pairs is, the higher the VC diffusion is. It is expected that this study can provide a theoretical direction for the experiments on the mass transfer of VC in water solution.

Vibrational Properties of Vacancy in Na and K Using MEAM Potential

The modified embedded atom method(MEAM)with the universal form of embedding function and a modified energy term along with the pair potential has been employed to determine the potentials for alkali metals:Na,K,by fitting to the Cauchy pressure(C_(12)−C_(44))/2,shear constants Gv=(C_(11)−C_(12)+3C_(44))/5 and C_(44),the cohesive energy and the vacancy formation energy.The obtained potentials are used to calculate the phonon dispersions of these metals.Using these calculated phonons we evaluate the local density of states of neighbours of vacancy using Green’s function method.The local density of states of neighbours of vacancy has been used to calculate mean square displacements of these atoms and formation entropy of vacancy.The calculated mean square displacements of both 1st and 2nd neighbours of vacancy are found to be lower than that of host atom.The calculated phonon dispersions agree well with the experimental phonon dispersion curves and the calculated results of vacancy formation entropy compare well with the other available results.