Stereoelectronic effects on molecular geometries and state-energy splittings of ligated monocopper dioxygen complexes

The relative energies of side-on versus end-on binding of molecular oxygen to a supported Cu(I) species, and the singlet versus triplet nature of the ground electronic state, are sensitive to the nature of the supporting ligands and, in particular, depend upon their geometric arrangement relative to the O2 binding site. Highly correlated ab initio and density functional theory electronic structure calculations demonstrate that optimal overlap (and oxidative charge transfer) occurs for the side-on geometry, and this is promoted by ligands that raise the energy, thereby enhancing resonance, of the filled Cu dxz orbital that hybridizes with the in-plane pi* orbital of O2. Conversely, ligands that raise the energy of the filled Cu dz2 orbital foster a preference for end-on binding as this is the only mode that permits good overlap with the in-plane O2 pi*. Because the overlap of Cu dz2 with O2 pi* is reduced as compared to the overlap of Cu dxz with the same O2 orbital, the resonance is also reduced, leading to generally more stable triplet states relative to singlets in the end-on geometry as compared to the side-on geometry, where singlet ground states become more easily accessible once ligands are stronger donors. Biradical Cu(II)-O2 superoxide character in the electronic structure of the supported complexes leads to significant challenges for accurate quantum chemical calculations that are best addressed by exploiting the spin-purified M06L local density functional, single-reference completely renormalized coupled-cluster theory, or multireference second-order perturbation theory, all of which provide predictions that are qualitatively and quantitatively consistent with one another.     

Catalyst‐free Efficient Synthesis of 3‐Thio‐2‐deoxysugar Derivatives in Water

3‐Thio‐ and 3‐dithiocarbamoyl‐2‐deoxy carbohydrate derivatives have been synthesized using water as solvent without using a catalyst. In most of the cases yields obtained were excellent.     

Prion protein self-peptides modulate prion interactions and conversion

Background  

Molecular mechanisms underlying prion agent replication, converting host-encoded cellular prion protein (PrP^C) into the scrapie associated isoform (PrP^Sc), are poorly understood. Selective self-interaction between PrP molecules forms a basis underlying the observed differences of the PrP^C into PrP^Sc conversion process (agent replication). The importance of previously peptide-scanning mapped ovine PrP self-interaction domains on this conversion was investigated by studying the ability of six of these ovine PrP based peptides to modulate two processes; PrP self-interaction and conversion.     

Efficient formulation and computer implementation of the active-space electron-attached and ionized equation-of-motion coupled-cluster methods

The efficient, general-purpose implementations of the active-space electron-attached (EA) and ionized (IP) equation-of-motion coupled-cluster (EOMCC) methods including up to 3p-2h and 3h-2p excitations, called EA-EOMCCSDt and IP-EOMCCSDt, respectively, are discussed. The details of the algorithm that enables one to achieve a high degree of code vectorization for the active-space methods and the factorized forms of the EA- and IP-EOMCCSDt equations that maximize the benefits of using active orbitals in the process of selecting the dominant 3p-2h and 3h-2p excitations are presented. The results of benchmark calculations for the low-lying doublet and quartet states of the CH and SH radicals reveal that the active-space EA-EOMCCSDt and IP-EOMCCSDt methods are capable of producing results for the electronic excitations in open-shell systems that match the high accuracy of EA- and IP-EOMCC calculations with a full treatment of 3p-2h and 3h-2p excitations, even when the excited states of interest display a manifestly multideterminantal nature, with the costs that can be on the same order of those characterizing the basic EOMCC singles and doubles approach.     

Evolution and symmetry of multipartite entanglement

We discover a simple factorization law describing how multipartite entanglement of a composite quantum system evolves when one of the subsystems undergoes an arbitrary physical process. This multipartite entanglement decay is determined uniquely by a single factor we call the entanglement resilience factor. Since the entanglement resilience factor is a function of the quantum channel alone, we find that multipartite entanglement evolves in exactly the same way as bipartite (two qudits) entanglement. For the two qubits case, our factorization law reduces to the main result of [T. Konrad, Nature Phys. 4, 99 (2008)10.1038/nphys885]. In addition, for a permutation P, we provide an operational definition of P asymmetry of entanglement, and find the conditions when a permuted version of a state can be achieved by local means.     

Analysis of a fuzzy economic order quantity model for deteriorating items under retailer partial trade credit financing in a supply chain

This paper investigates the economic order quantity (EOQ) — based inventory model for a retailer under two levels of trade credit to reflect the supply chain management situation in the fuzzy sense. It is assumed that the retailer maintains a powerful position and can obtain the full trade credit offered by the supplier yet the retailer just offers a partial trade credit to customers. The demand rate, holding cost, ordering cost, purchasing cost and selling price are taken as fuzzy numbers. Under these conditions, the retailer can obtain the most benefits. Study also investigates the retailer’s inventory policy for deteriorating items in a supply chain management situation as a cost minimization problem in the fuzzy sense. The annual total variable cost for the retailer in fuzzy sense is defuzzified using Graded Mean Integration Representation method. Then the present study shows that the defuzzified annual total variable cost for the retailer is convex, that is, a unique solution exists. Mathematical theorems and algorithms are developed to efficiently determine the optimal inventory policy for the retailer. Numerical examples are given to illustrate the theorems and the algorithms. Finally, the results in this paper generalize some already published results in the crisp sense.     

A convenient room temperature ipso‐nitration of arylboronic acid catalysed by molecular iodine using zirconium oxynitrate as nitrating species: An experimental and theoretical investigation

A simple and convenient protocol has been developed for ipso‐nitration of arylboronic acid catalysed by molecular iodine at room temperature, using zirconium oxynitrate as the nitrating species. The protocol is applicable to electronically diverse aryl‐ and heteroarylboronic acid moieties under mild reaction conditions with good to excellent isolated yields. Furthermore, a theoretical investigation has been performed for the same reaction, and reaction profiles are modelled using modern density functional theory (DFT). DFT‐based results support the experimentally observed results.