Hamilton-Jacobi formulation of Kolmogorov-Sinai entropy for classical and quantum dynamics

A Hamilton-Jacobi formulation of the Lyapunov spectrum and Kolmogorov-Sinai (KS) entropy is developed. It is numerically efficient and reveals a close relation between the KS invariant and the classical action. This formulation is extended to the quantum domain using the Madelung-Bohm orbits associated with the Schroedinger equation. The resulting quantum KS invariant for a given orbit equals the mean decay rate of the probability density along the orbit, while its ensemble average measures the mean growth rate of configuration-space information for the quantum system.     

Improved parameterization of the quantum harmonic oscillator model based on localized wannier functions to describe Van der Waals interactions in density functional theory

Recently, the quantum harmonic oscillator model has been combined with maximally localized Wannier functions to account for long‐range dispersion interactions in density functional theory calculations (Silvestrelli, J. Chem. Phys. 2013, 139, 054106). Here, we present a new, improved set of values for the three parameters involved in this scheme. To test the new parameter set we have computed the potential energy curves for various systems, including an isolated Ar2 dimer, two N2 dimers interacting within different configurations, and a water molecule physisorbed on pristine graphene. While the original set of parameters generally overestimates the interaction energies and underestimates the equilibrium distances, the new parameterization substantially improves the agreement with experimental and theoretical reference values. © 2016 Wiley Periodicals, Inc.     

Detection of hydrogen peroxide produced at a liquid/liquid interface using scanning electrochemical microscopy

Scanning electrochemical microscopy (SECM) was used to monitor in situ hydrogen peroxide (H₂O₂) produced at a polarized water/1,2-dichloroethane (DCE) interface. The water/DCE interface was formed between a DCE droplet containing decamethylferrocene (DMFc) supported on a solid electrode and an acidic aqueous solution. H₂O₂ was generated by reducing oxygen with DMFc at the water/DCE interface, and was detected with a SECM tip positioned in the vicinity of the interface using a substrate generation/tip collection mode. This work shows unambiguously how the H₂O₂ generation depends on the polarization of the liquid/liquid interface, and how proton-coupled electron transfer reactions can be controlled at liquid/liquid interfaces.     

Hydrogen Evolution at Liquid–Liquid Interfaces

Blowing bubbles : Hydrogen evolution by proton reduction with [(C₅Me₅)₂Fe] occurs at a soft interface between water and 1,2‐dichloroethane (DCE). The reaction proceeds by proton transfer assisted by [(C₅Me₅)₂Fe] across the water–DCE interface with subsequent proton reduction in DCE. The interface essentially acts as a proton pump, allowing hydrogen evolution by directly using the aqueous proton.

     

Universal measure of entanglement

A general framework is developed for separating classical and quantum correlations in a multipartite system. Entanglement is defined as the difference in the correlation information encoded by the state of a system and a suitably defined separable state with the same marginals. A generalization of the Schmidt decomposition is developed to implement the separation of correlations for any pure, multipartite state. The measure based on this decomposition is a generalization of the entanglement of formation to multipartite systems, provides an upper bound for the relative entropy of entanglement, and is directly computable on pure states. The example of pure three-qubit states is analyzed in detail, and a classification based on minimal, four-term decompositions is developed.     

Investigation of structure of milled wood and dioxane lignins of Populus nigra and Cupressus sempervirens using the DFRC method

In this study, derivatisation followed by reductive cleavage (DFRC) were used to investigate milled wood lignin (MWL) and dioxane lignin (DL) structures of Populus nigra and Cupressus sempervirens. After the DFRC reactions, the constituents obtained from these two kinds of lignin were recognised structurally using several chromatographic and spectral methods such as ¹³C NMR, GC-MS, and GPC. Comparative results showed that the dominant structural components of the two kinds of lignin are obtained from the cleavage of ??-O-4 bonds. The main component of DL and MWL of P. nigra is 4-hydroxy-3,5-dimethoxy-1-phenyl-??-hydroxypropene (syringyl structures). Also, some guaiacyl structures were observed. The dominant component identified in both lignins of C. sempervirens is 4-hydroxy-3-methoxy-1-phenyl-??-hydroxypropene (guaiacyl structures). The cleavage method has a good performance for both P. nigra and C. sempervirens and the results obtained are in good agreement with previously published data.