Evaluation of dynamical properties of open quantum systems using the driven Liouville-von Neumann approach: methodological considerations

Methodological aspects of using the driven Liouville-von Neumann (DLvN) approach for simulating dynamical properties of molecular junctions are discussed. As a model system we consider a non-interacting resonant level uniformly coupled to a single Fermionic bath. We demonstrate how a finite system can mimic the depopulation dynamics of the dot into an infinite band bath of continuous and uniform density of states. We further show how the effects of spurious energy resolved currents, appearing due to the approximate nature of the equilibrium state obtained in DLvN calculations, can be avoided. Several ways to approach the wide band limit, which is often adopted in analytical treatments, using a finite numerical model system are discussed including brute-force increase of the lead model bandwidth as well as efficient cancellation or direct subtraction of finite-bandwidth effect. These methodological considerations may be relevant also for other numerical schemes that aim to study non-equilibrium thermodynamics via simulations of open quantum systems.     

Grafted poly(1→4-β-glucan) strands on silica: a comparative study of surface reactivity as a function of grafting density

Grafted poly(β-glucan) (β-glu) strands on the surface of silica are synthesized with varying degrees of grafting density, and display an amorphous-like environment via (13)C CP/MAS NMR spectroscopy. Thermal gravimetric analysis of these materials under oxidative conditions shows increased β-glu thermal stability with higher degrees of grafting density. The range of temperature stability between the most and least hydrogen-bound grafted β-glu strands spans 321 to 260 °C. This range is bound by the combustion temperature previously measured for crystalline and amorphous cellulose, with the former having greater oxidative stability, and is likely controlled by the extent of hydrogen bonding of a grafted β-glu strand with the underlying silica surface. When using these materials as reactants for glycosidic bond hydrolysis, the total number of reducing ends formed during reaction is quantified using a BCA colorimetric assay. Results demonstrate that the material with greatest interaction with silica surface silanols undergoes hydrolysis at an initial rate that is 6-fold higher than the material with the lowest degree of such interaction. The role of the surface as a reactive interface that can endow oxidative stability and promote hydrolysis activity has broad implications for surface-catalyzed processes dealing with biomass-derived polymers.     

Competition of ester, amide, ether, carbonate, alcohol and epoxide ligands in the dirhodium experiment (chiral discrimination by NMR spectroscopy)

Thirty-eight derivatives of 3-hydroxy-2-methylpropanoic acid, each with two different oxygen functionalities, were synthesized and subjected to the standard dirhodium experiment (1H NMR in the presence of an equimolar amount of the chiral dirhodium tetracarboxylate complex Rh*). Their structures represent ester, amide, carbonate, ether, alcohol and/or epoxy groups. Significant selectivity in the binding of those oxygen groups to the complex were determined. From these results, a priority list in binding to a rhodium atom of Rh* was established: epoxides > primary alcohols > ethers > or = esters > or = amides > carbonates > tertiary alcohols. This sequence allows the prediction of the preferred binding site of oxygen-containing groups in polyfunctional compounds, which frequently occur among natural products, and, particularly, in asymmetric synthesis of such compounds. Differentiation of the enantiomers by the dirhodium experiment is easily accomplished due to numerous signal dispersions in nearly all cases.     

Modal theory for the two-frequency mutual coherence function in random media: general theory and plane wave solution: II

In a previous publication (part I) it has been shown that for an arbitrary statistically isotropic and homogeneous medium the parabolic equation for the two-frequency mutual coherence function can be separated and thereby expressed as a superposition of modes. A parameterization based on the longitudinal part of this representation has also been treated. This paper explores the transverse structure and parameterization of the field solution by employing dimensional, variational and the modified WKB procedures for solving the eigenfunction/eigenvalue problem. General expressions are derived first for a general structure function and then specialized for a power-law structure function with emphasis on quadratic and Kolmogorov media.     

Nuclear orbiting and anomalies in nuclear reactions

In this paper, we report our measurements of back-angle oxygen and carbon particle yields from ¹⁶O+⁸⁹Y, ¹²C+⁹³Nb reactions forming the same compound nucleus ¹⁰⁵Ag at the same excitation energy and spin distribution. We find anomalously large oxygen yield and entrance channel dependence at high excitation energies from ¹⁶O+⁸⁹Y reaction implying formation of a dinuclear orbiting complex. Possible connection between nuclear orbiting and fast fission is also discussed.     

Kinetic salt effects on the outer sphere electron transfer reaction between hexacyanoferrate(II) and 4-pyridinecarboxylatopentammine cobalt(III)

A study is made of the kinetic salt effects upon the outer-sphere electron transfer reaction between hexacyanoferrate(II) and 4-pyridinecarboxylatopentaamminecobalt(III). The observed salts effects are analyzed, taking into account the possible association of the reactants with the ions of the supporting electrolyte, though no conclusive results could be obtained. A correlation has been established between the logarithm of the observed second-order rate constants and the logarithm of the rate constants for a related innersphere electron transfer reaction. From this correlation the conclusion can be drawn that the observed salt effects in concentrated electrolyte solutions are mainly due to the effects on the electron transfer step. © John Wiley & Sons, Inc.     

Characterization of Volatile Flavor Compounds in Supercritical Fluid Separated and Identified in Gurum (Citrulluslanatus Var. colocynthoide) Seed Oil Using HSME and GC–MS

In this study, the volatile compound profiles of gurum seed oil were determined using two methods: supercritical CO₂ extraction (SFE) and the screw press process (SPP). For volatile compounds extraction and identification, headspace solid-phase micro-extraction (HS-SPME) and GC–MS were used, respectively. A total number of 56 volatile compounds were revealed and identified in oil extracted by SFE, while only 40 compounds were detected in extracted oil by SPP. Acids, aldehydes, esters, ketones, furans, and other components were present in the highest ratio in oil extracted by SFE. In contrast, alcohols and alkenes were found in the highest proportion in oil extracted by SPP. In this study, it was observed that SFE showed an increase in the amounts of volatile compounds and favorably impacted the aroma of gurum seed oil. The results reveal that different extraction methods significantly impact the volatile components of gurum seed oil, and this study can help evaluate the quality of the oil extracted from gurum seeds.