Semiclassical nonadiabatic dynamics based on quantum trajectories for the O(3P,1D) + H2 system

The O(3P,1D) + H2 --> OH + H reaction is studied using trajectory dynamics within the approximate quantum potential approach. Calculations of the wave-packet reaction probabilities are performed for four coupled electronic states for total angular momentum J = 0 using a mixed coordinate/polar representation of the wave function. Semiclassical dynamics is based on a single set of trajectories evolving on an effective potential-energy surface and in the presence of the approximate quantum potential. Population functions associated with each trajectory are computed for each electronic state. The effective surface is a linear combination of the electronic states with the contributions of individual components defined by their time-dependent average populations. The wave-packet reaction probabilities are in good agreement with the quantum-mechanical results. Intersystem crossing is found to have negligible effect on reaction probabilities summed over final electronic states.     

Molecular dynamics studies of ion distributions for DNA duplexes and DNA clusters: salt effects and connection to DNA melting

We present extensive molecular dynamics simulations of the ion distributions for DNA duplexes and DNA clusters using the Amber force field with implicit water. The distribution of ions and the electrostatic energy of ions around an isolated DNA duplex and clusters of DNA duplexes in different salt (NaCl) concentrations over the range 0.2-1.0 mol/L are determined on the basis of the simulation results. Using the electrostatic energy profile, we determine a local net charge fraction phi, which is found to increase with increasing of salt concentration. For DNA clusters containing two DNA duplexes (DNA pair) or four DNA duplexes, phi increases as the distance between the duplexes decreases. Combining this result with experimental results for the dependence of the DNA melting temperature on bulk salt concentration, we conclude that for a pair of DNA duplexes the melting temperature increases by 5-10 K for interaxis separations of 25-40 A. For a cluster of four DNA duplexes, an even larger melting temperature increase should occur. We argue that this melting temperature increase in dense DNA clusters is responsible for the cooperative melting mechanism in DNA-linked nanoparticle aggregates and DNA-linked polymer aggregates.     

Working group report: Heavy-ion physics and quark-gluon plasma

This is the report of Heavy Ion Physics and Quark-Gluon Plasma at WHEPP-09 which was part of Working Group-4. Discussion and work on some aspects of quark-gluon plasma believed to have created in heavy-ion collisions and in early Universe are reported.     

Coaxing Solid‐State Phosphorescence from Tellurophenes

The synthesis of the first examples of tellurophenes exhibiting phosphorescence in the solid state and under ambient conditions (room temperature and in air) is reported. Each of these main‐group‐element‐based emitters feature pinacolboronates (BPin) as ring‐appended side groups. The nature of the luminescence observed was also investigated using computational methods.     

Atomistic molecular dynamics simulations of peptide amphiphile self-assembly into cylindrical nanofibers

Relaxation of a self-assembled structure of 144 peptide amphiphile (PA) molecules into cylindrical nanofibers is studied using atomistic molecular dynamics simulations including explicit water with physiological ion concentration. The PA for these studies includes a hydrophobic alkyl chain that is attached to the N-terminus of the sequence SLSLAAAEIKVAV. The self-assembly is initiated with PA molecules in a roughly cylindrical configuration, as suggested from previous experimental and theoretical investigations, and the cylindrical configuration that results is found to be stable during 40 ns simulations. In the converged structure of the resulting nanofiber, the cylinder radius is ～44 ?, a result that is consistent with experimental results. Water and sodium ions can penetrate into the peptide portion of the fiber but not between the alkyl chains. Even though each PA has an identical sequence, a broad distribution of secondary structure is found in the converged structure of the nanofiber. The β-sheet population for the SLSL and IKV segments of the peptide is ～25%, which is consistent with previous circular dichroism results. We also found that the epitope sequence IKVAV is located on the surface of the nanofiber, as designed for the promotion of the neurite growth. Our findings will be useful for designing new PA fibers that have improved bioactive properties.     

Extensive scaling from computational homology and Karhunen-Loève decomposition analysis of Rayleigh-Bénard convection experiments

Spatiotemporally chaotic dynamics in laboratory experiments on convection are characterized using a new dimension, D(CH), determined from computational homology. Over a large range of system sizes, D(CH) scales in the same manner as D(KLD), a dimension determined from experimental data using Karhuenen-Loéve decomposition. Moreover, finite-size effects (the presence of boundaries in the experiment) lead to deviations from scaling that are similar for both D(CH) and D(KLD). In the absence of symmetry, D(CH) can be determined more rapidly than D(KLD).     

Control of the PEO chain conformation on nanoparticles by adsorption of PEO-block-poly(L-lysine) copolymers and its significance on colloidal stability and protein repellency

The physical adsorption of PEO(n)-b-PLL(m) copolymers onto silica nanoparticles and the related properties of poly(ethylene oxide) (PEO)-coated particles were studied as a function of the block copolymer composition. Copolymers adopt an anchor-buoy conformation at the particle surface owing to a preferential affinity of poly(L-lysine) (PLL) blocks with the silica surface over PEO blocks when a large excess of copolymer is used. The interdistance between PEO chains at particle surface is highly dependent on the size of PLL segments; a dense brush of PEO is obtained for short PLL blocks (DP = 10), whereas PEO chains adopt a so-called interacting "mushroom" conformation for large PLL blocks (DP = 270). The size of the PEO blocks does not really influence the copolymer surface density, but it has a strong effect on the PEO layer thickness as expected. Salt and protein stability studies led to similar conclusions about the effectiveness of a PEO layer with a dense brush conformation to prevent colloidal aggregation and protein adsorption. Besides, a minimal PEO length is required to get full stabilization properties; as a matter of fact, both PEO(45)-b-PLL(10) and PEO(113)-b-PLL(10) give rise to a PEO brush conformation but only the latter copolymer efficiently stabilizes the particles in the presence of salt or proteins.     

Absorption and magnetic circular dichroism spectra of Cs2ZrBr6: Os4+

High resolution absorption and magnetic circular dichroism (M.C.D.) spectra for Cs₂ZrBr₆ : Os⁴⁺ are reported at liquid helium temperature over the range 17 000–31 000 cm^-1. These results in conjunction with previous work on Cs₂ZrCl₆ : Os⁴⁺ provide a study of the Os⁴⁺ spectrum as a function of ligand spin-orbit coupling constant. The present results strongly support the previous ligand-to-metal charge-transfer interpretation formulated in the j-j limit, described by Piepho et al. [6]. The strong absorption bands can be assigned with confidence to specific, allowed charge-transfer transitions, and detailed assignments are suggested for the less intense features on the basis of forbidden (vibrationally-induced) charge-transfer transitions. Aside from the low energy region (? 16 000 cm^-1) not reported in this work, there seems to be no reason for assigning any important spectral features to d →d transitions.     

Hölder estimates for Green’s functions on convex polyhedral domains and their applications to finite element methods

A model second-order elliptic equation on a general convex polyhedral domain in three dimensions is considered. The aim of this paper is twofold: First sharp Hölder estimates for the corresponding Green’s function are obtained. As an applications of these estimates to finite element methods, we show the best approximation property of the error in \({W^1_{\infty}}\) . In contrast to previously known results, \({W_p^{2}}\) regularity for p > 3, which does not hold for general convex polyhedral domains, is not required. Furthermore, the new Green’s function estimates allow us to obtain localized error estimates at a point.