Characterization of a Robust CoII Fluorescent Complex Deposited Intact On HOPG

The new diimine fluorescent ligand ACRI‐1 based on a central acridine yellow core is reported along with its coordination complex [Co₂( ACRI‐1 )₂] ( 1 ), a fluorescent weak ferromagnet. Due to the strong fluorescence of the acridine yellow fluorophore, it is not completely quenched when the ligand is coordinated to Co^II. The magnetic properties of bulk complex 1 and its stability in solution have been studied. Complex 1 has been deposited on highly ordered pyrolitic graphite (HOGP) from solution. The thin films prepared have been characterized by AFM, time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS), grazing incidence X‐ray diffraction (GIXRD), X‐ray absorption spectroscopy (XAS), X‐ray magnetic circular dichroism (XMCD) and theoretical calculations. The data show that the complex is robust and remains intact on the surface of graphite.     

Can CH⋅⋅⋅π Interactions Be Used To Design Single‐Chain Magnets?

This theoretical study suggests that CH???π stacking interactions between monomeric units can be used to design novel single‐chain magnets (SCMs), as the sign of coupling is predictable and such chains inherently yield negative axial anisotropy, a condition often difficult to achieve in conventional SCMs.     

Magnetic Relaxation in Single‐Electron Single‐Ion Cerium(III) Magnets: Insights from Ab Initio Calculations

Detailed ab initio calculations were performed on two structurally different cerium(III) single‐molecule magnets (SMMs) to probe the origin of magnetic anisotropy and to understand the mechanism of magnetic relaxations. The complexes [Ce^III{Zn^II(L)}₂(MeOH)]BPh₄ ( 1 ) and [Li(dme)₃][Ce^III(cot′′)₂] ( 1 ; L=N,N,O,O‐tetradentate Schiff base ligand; 2 ; DME=dimethoxyethane, COT′′=1,4‐bis(trimethylsilyl)cyclooctatetraenyldianion), which are reported to be zero‐field and field‐induced SMMs with effective barrier heights of 21.2 and 30 K respectively, were chosen as examples. CASSCF+RASSI/SINGLE_ANISO calculations unequivocally suggest that m_J|±5/2〉 and |±1/2〉 are the ground states for complexes 1 and 2 , respectively. The origin of these differences is rooted back to the nature of the ligand field and the symmetry around the cerium(III) ions. Ab initio magnetisation blockade barriers constructed for complexes 1 and 2 expose a contrasting energy‐level pattern with significant quantum tunnelling of magnetisation between the ground state Kramers doublet in complex 2 . Calculations performed on several model complexes stress the need for a suitable ligand environment and high symmetry around the cerium(III) ions to obtain a large effective barrier.     

Quantitative determination of tri-n-butyl phosphate by fluorescent X-ray spectrometry through inorganic association with an actinide

Tri-n-butyl phosphate (TBP) continues to be the most widely used solvent in nuclear fuel extraction, refining and reprocessing units for the extraction of actinides and their separation from fission products. An X-ray fluorescence spectrometric method (XRFS) for the determination of TBP content with an X-ray detectable element is presented. The method involves formation of an ion association complex of uranium with TBP-kerosene mixture in 3M nitric acid. The analytes uranium and bromine used as internal ratio elements in organic extract are excited by a primary X-ray beam from a rhodium tube. The solvent concentration is determined from the ratioed characteristic intensities of uranium and bromine. The procedure permits the determination of organic solvent in the range 0.5 to 5.0% with a relative standard deviation of 0.1%.     

An ab initio and DFT study on the hydrolysis of carbonyl dichloride

Hydrolysis of carbonyl dichloride or phosgene (Cl₂CO) in gas phase has been investigated at Hartree–Fock, density functional and ab initio levels of theory. The effects of basis sets on the energetics of the reaction have also been explored. Calculations reveal that initially carbonyl dichloride and water form a weak complex and this complex can react further in two ways. In Path 1, water adds on to carbonyl dichloride across carbonyl bond in a concerted fashion to give dichloromethane diol, and this diol decomposes to form chloro formic acid by syn-1,2-elimination of HCl and forms CO₂ and HCl as final products. Path 2 is the concerted addition of water across carbon chlorine bond and elimination of HCl in a single step leading to the formation of chloro formic acid directly. This second path that skips the formation of dichloromethane diol is observed to be very low lying and hence is kinetically favored. Addition of second water molecule to the reacting system is found to catalyze the reaction by stabilizing the complex, intermediate and transition states and reduces the activation energy to 24.6 kcal mol⁻¹ compared to 29.9 kcal mol⁻¹ for a single water molecule.     

Analysis of algorithms for an online version of the convoy movement problem

In the convoy movement problem (CMP), a set of convoys must be routed from specified origins to destinations in a transportation network, represented by an undirected graph. Two convoys may not cross each other on the same edge while travelling in opposing directions, a restriction referred to as blocking. However, convoys are permitted to follow each other on the same edge, with a specified headway separating them, but no overtaking is permitted. Further, the convoys to be routed are distinguished based on their length. Particle convoys have zero length and are permitted to traverse an edge simultaneously, whereas convoys with non-zero length have to follow each other, observing a headway. The objective is to minimize the total time taken by convoys to travel from their origins to their destinations, given the travel constraints on the edges. We consider an online version of the CMP where convoy demands arise dynamically over time. For the special case of particle convoys, we present an algorithm that has a competitive ratio of 3 in the worst case and (5/2) on average. For the particle convoy problem, we also present an alternate, randomized algorithm that provides a competitive ratio of (√13?1). We then extend the results to the case of convoys with length, which leads to an algorithm with an O(T+CL) competitive ratio, where T={Max _e t(e)}/{Min _e t(e)}, C is the maximum congestion (the number of distinct convoy origin–destination pairs that use any edge e) and L={Max _c L(c)}/{Min _c L(c)}; here L(c)>0 represents the time-headway to be observed by any convoy that follows c and t(e) represents the travel time for a convoy c on edge e.     

Solitons and critical breakup fields in lithium niobate type uniaxial ferroelectrics

Ferroelectric materials, such as lithium niobate, show interesting non-linear hysteresis behavior that can be explained by a dynamical system analysis. By using variational principle, a non-linear Klein-Gordon (K-G) equation is derived for lithium niobate type of uniaxial ferroelectrics involving various types of energy, which was not considered previously to construct the Hamiltonian. This leads to soliton solutions under different conditions of soliton velocity. The critical value of the (dimensional) effective electric field has been estimated to be 54–58 kV/cm for lithium niobate depending on the impurity content in these type inhomogeneous ferroelectrics. Beyond this critical field, there is no existence of solitons. This critical field is related to a break-up mechanism of Landau-Ginzburg two-well potential to a single well, as the driving force is increased.