Predicting hydration free energies of polychlorinated aromatic compounds from the SAMPL-3 data set with FiSH and LIE models

Next-generation solvation models are devised to mimic the accuracy and generality of explicit solvation models at the speed of current popular implicit solvation models. One such method is the first-shell of hydration (FiSH) continuum model that was trained on hydration energetics from LIE calculations and molecular dynamics simulations in explicit solvent. Here we tested prospectively the FiSH model on the SAMPL-3 hydration data set that zooms in the effect of chlorination on solvation. We compare these FiSH predictions with those from retrospective LIE calculations. We find that neither FiSH nor LIE can reproduce well the absolute values and the trend of hydration free energies in the biphenyl and dioxin aromatic chlorination series. Some of the hypotheses behind this performance are discussed and tested. The LIE explicit-solvent model shows some improvement relative to the FiSH continuum model, and we correct a systematic deviation in the continuum van der Waals term of FiSH associated with aromatic Cl atom type.     

One- and two-photon induced emission in heterobimetallic Zn(II)-Sm(III) and Zn(II)-Tb(III) complexes with a side-off compartmental ligand

Heterobimetallic [Zn(II)Ln(III)] complexes have been obtained using a compartmental Schiff-base ligand, H(2)valdmpn, resulting from the 2:1 condensation between o-vanillin and 2,2-dimethyl-propilenediamine: [Zn(H(2)O)(valdmpn)Sm(O(2)NO)(3)] 1, [Zn(H(2)O)(valdmpn)Tb(O(2)NO)(3)] 2a, [Zn(H(2)O)(valdmpn)Tb(O(2)NO)(3)]·H(2)O 2b, and [Zn(H(2)O)(valdmpn)Gd(O(2)NO)(3)]·H(2)O 3. The crystal structures of 1, 2b, and 3 have been solved. Compounds 1 and 2a crystallize in a non-centrosymmetric space group (P2(1)2(1)2(1)), being isomorphous. Crystals 2b and 3 are also isomorphous (space group P1[combining macron]). The complex entities in the four crystals are similar and their structures consist of binuclear species with the pentacoordinated zinc(II) ion hosted into the N(2)O(2) compartment and the lanthanide(III) ion in the large, open compartment, with a coordination number of 10. The photophysical properties of the four compounds have been investigated. Strong visible excited (excitation tails extend up to 420-430 nm) one photon antenna sensitization was obtained with the samarium(III) and terbium(III) derivatives. Following femtosecond Ti:Sapphire laser at λ(ex) = 775 nm, both second-harmonic generation at λ(em) = 775/2 nm and two-photon induced emission in the VIS range were obtained, extending thus the excitation range of these complexes from the VIS to the NIR spectral range. The two-photon induced emission and second harmonic generation effect for a samarium(III) complex are reported for the first time.     

On securitization,market completion and equilibrium risk transfer

We propose an equilibrium framework within which to price financial securities written on non-tradable underlyings such as temperature indices. We analyze a financial market with a finite set of agents whose preferences are described by a convex dynamic risk measure generated by the solution of a backward stochastic differential equation. The agents are exposed to financial and non-financial risk factors. They can hedge their financial risk in the stock market and trade a structured derivative whose payoff depends on both financial and external risk factors. We prove an existence and uniqueness of equilibrium result for derivative prices and characterize the equilibrium market price of risk in terms of a solution to a non-linear BSDE.     

Objective molecular dynamics

We introduce a generalization of periodic molecular dynamics that we term objective molecular dynamics. It is a method of doing molecular dynamics for a restricted set of atoms, nonperiodically mapping the time-dependent displacements of this small set of atoms onto the full, typically infinite structure, such that the full structure satisfies exactly the full, unconstrained set of equations of molecular dynamics subject to certain group-invariant initial conditions. The method is applicable to a wide variety of interesting molecular structures including the tails, capsids and other parts of many viruses, carbon nanotubes, many of the common proteins, C₆₀ and many other nanostructures now being synthesized, especially via the process of self-assembly. The method is illustrated by simulations of carbon nanotubes.     

Thermal properties of EPDM/NR blends

The thermal behaviour of EPDM/NR blends was studied by differential scanning calorimetry over the temperature range 335–435 K. O'Neill's method (O'Neill MG. Anal Chem 1964;36:1238) was used for calculating the specific heat capacity with aluminia as standard. The presence of natural rubber induces a marked thermal instability because of the high content of double bonds. The contribution of each component to the C_p of the tested polymer systems is discussed. The law of reciprocal affinity, the linear contribution of components to the specific heat capacity is followed by EPDM/NR blends. The influence of natural rubber on the thermal behaviour of tested mixtures was assessed by oxygen uptake method and the first derivative procedure reveals the sequence in thermal stability of ethylene-propylene-diene/natural rubber compounds.     

Selective cap opening in carbon nanotubes driven by laser-induced coherent phonons

We demonstrate the possibility of a selective nonequilibrium cap opening of carbon nanotubes as a response to femtosecond laser excitation. By performing molecular dynamics simulations based on a microscopic electronic model we show that the laser-induced ultrafast structural changes differ dramatically from the thermally induced dimer emission. Ultrafast bond weakening and simultaneous excitation of two coherent phonon modes of different frequencies, localized in the spherical caps and cylindrical nanotube body, are responsible for the selective cap opening.     

Artificial viscosity proper orthogonal decomposition

We introduce improved reduced-order models for turbulent flows. These models are inspired from successful methodologies used in large eddy simulation, such as artificial viscosity, applied to standard models created by proper orthogonal decomposition of flows coupled with Galerkin projection. As a first step in the analysis and testing of our new methodology, we use the Burgers equation with a small diffusion parameter. We present a thorough numerical analysis for the time discretization of the new models. We then test these models in two problems displaying shock-like phenomena. Of course, since the Burgers equation does not model turbulence, we next need to test our new models in realistic turbulent flow settings. This is the subject of a forthcoming report.