On the Molecular Origin of the Cooperative Coil-to-globule Transition of Poly(N-isopropylacrylamide) in Water

By means of atomistic molecular dynamics simulations we investigate the behaviour of poly(N-isopropylacrylamide), PNIPAM, in water at temperatures below and above the lower critical solution temperature (LCST), including the undercooled regime. The transition between water soluble and insoluble states at the LCST is described as a cooperative process involving an intramolecular coil-to-globule transition preceding the aggregation of chains and the polymer precipitation. In this work we investigate the molecular origin of such cooperativity and the evolution of the hydration pattern in the undercooled polymer solution. The solution behaviour of an atactic 30-mer at high dilution is studied in the temperature interval from 243 to 323 K with a favourable comparison to available experimental data. In the PNIPAM water soluble states we detect a correlation between polymer segmental dynamics and diffusion motion of bound water, occurring with the same activation energy. Simulation results show that below the coil-to-globule transition temperature PNIPAM is surrounded by a network of hydrogen bonded water molecules and that the cooperativity arises from the structuring of water clusters in proximity to hydrophobic groups. Differently, the perturbation of the hydrogen bond pattern involving water and amide groups occurs above the transition temperature. Altogether these findings reveal that even above the LCST PNIPAM remains largely hydrated and that the coil-to-globule transition is related with a significant rearrangement of the solvent in proximity of the surface of the polymer. The comparison between the hydrogen bonding of water in the surrounding of PNIPAM isopropyl groups and in bulk displays a decreased structuring of solvent at the hydrophobic polymer-water interface across the transition temperature, as expected because of the topological extension along the chain of such interface

Numerical Simulations of the Dark Universe: State of the Art and the Next Decade

We present a review of the current state of the art of cosmological dark matter simulations, with particular emphasis on the implications for dark matter detection efforts and studies of dark energy. This review is intended both for particle physicists, who may find the cosmological simulation literature opaque or confusing, and for astro-physicists, who may not be familiar with the role of simulations for observational and experimental probes of dark matter and dark energy. Our work is complementary to the contribution by M. Baldi in this issue, which focuses on the treatment of dark energy and cosmic acceleration in dedicated N-body simulations. Truly massive dark matter-only simulations are being conducted on national supercomputing centers, employing from several billion to over half a trillion particles to simulate the formation and evolution of cosmologically representative volumes (cosmic scale) or to zoom in on individual halos (cluster and galactic scale). These simulations cost millions of core-hours, require tens to hundreds of terabytes of memory, and use up to petabytes of disk storage. The field is quite internationally diverse, with top simulations having been run in China, France, Germany, Korea, Spain, and the USA. Predictions from such simulations touch on almost every aspect of dark matter and dark energy studies, and we give a comprehensive overview of this connection. We also discuss the limitations of the cold and collisionless DM-only approach, and describe in some detail efforts to include different particle physics as well as baryonic physics in cosmological galaxy formation simulations, including a discussion of recent results highlighting how the distribution of dark matter in halos may be altered. We end with an outlook for the next decade, presenting our view of how the field can be expected to progress. (abridged)Comment: 54 pages, 4 figures, 3 tables; invited contribution to the special issue "The next decade in Dark Matter and Dark Energy" of the new Open Access journal "Physics of the Dark Universe". Replaced with accepted versio

A hybrid stabilization technique for simulating water wave - Structure interaction by incompressible Smoothed Particle Hydrodynamics (ISPH) method

The Smoothed Particle Hydrodynamics (SPH) method is emerging as a potential tool for studying water wave related problems, especially for violent free surface flow and large deformation problems. The incompressible SPH (ISPH) computations have been found not to be able to maintain the stability in certain situations and there exist some spurious oscillations in the pressure time history, which is similar to the weakly compressible SPH (WCSPH). One main cause of this problem is related to the non-uniform and clustered distribution of the moving particles. In order to improve the model performance, the paper proposed an efficient hybrid numerical technique aiming to correct the ill particle distributions. The correction approach is realized through the combination of particle shifting and pressure gradient improvement. The advantages of the proposed hybrid technique in improving ISPH calculations are demonstrated through several applications that include solitary wave impact on a slope or overtopping a seawall, and regular wave slamming on the subface of open-piled structure

Unified Gas-kinetic Wave-Particle Methods III: Multiscale Photon Transport

In this paper, we extend the unified gas-kinetic wave-particle (UGKWP) method to the multiscale photon transport. In this method, the photon free streaming and scattering processes are treated in an un-splitting way. The duality descriptions, namely the simulation particle and distribution function, are utilized to describe the photon. By accurately recovering the governing equations of the unified gas-kinetic scheme (UGKS), the UGKWP preserves the multiscale dynamics of photon transport from optically thin to optically thick regime. In the optically thin regime, the UGKWP becomes a Monte Carlo type particle tracking method, while in the optically thick regime, the UGKWP becomes a diffusion equation solver. The local photon dynamics of the UGKWP, as well as the proportion of wave-described and particle-described photons are automatically adapted according to the numerical resolution and transport regime. Compared to the $S_n$ -type UGKS, the UGKWP requires less memory cost and does not suffer ray effect. Compared to the implicit Monte Carlo (IMC) method, the statistical noise of UGKWP is greatly reduced and computational efficiency is significantly improved in the optically thick regime. Several numerical examples covering all transport regimes from the optically thin to optically thick are computed to validate the accuracy and efficiency of the UGKWP method. In comparison to the $S_n$ -type UGKS and IMC method, the UGKWP method may have several-order-of-magnitude reduction in computational cost and memory requirement in solving some multsicale transport problems.Comment: 27 pages, 15 figures. arXiv admin note: text overlap with arXiv:1810.0598