Temperature Dependence of 1H Paramagnetic Chemical Shifts in Actinide Complexes,Beyond Bleaney's Theory: The AnVIO22+–Dipicolinic Acid Complexes (An=Np,Pu) as an Example

Actinide +VI complexes ( = , and ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, and complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the ¹H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans’ method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the complex. The temperature dependence of the pNMR chemical shifts has a strong contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the complex and a non-Kramers-doublet model for the complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center.     

Hybrid EuIII Coordination Luminophore Standing on Two Legs on Silica Nanoparticles for Enhanced Luminescence

In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent Ln^III-silica nanomaterials. A novel Eu^III-silica hybrid nanoparticle was developed by using a doubly binding TPPO−Si(OEt)₃ (TPPO: triphenyl phosphine oxide) linker. The TPPO−Si(OEt)₃ was confirmed by ¹H, ³¹P, ²⁹Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)₃ and Eu(tfc)₃ moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO−Si(OEt)₃-modified silica nanoparticles, producing Eu(hfa)₃(TPPO−Si)₂-SiO₂ and Eu(tfc)₃(TPPO−Si)₂-SiO₂, respectively. Eu(hfa)₃(TPPO−Si)₂−SiO₂ exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported Eu^III-based hybrid materials. Eu(tfc)₃(TPPO−Si)₂−SiO₂ showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)₃(TPPO−Si(OEt)₃)₂ was found to be 39 %. These results confirmed that the TPPO−Si(OEt)₃ linker is a promising candidate for development of Eu^III-based luminescent materials.     

Designing an all epitaxial 1,550 nm intra-cavity VCSEL using GaInAsN/AlGaInAs in the active region and AlGaAsSb/AlAsSb in top and bottom DBRs

In this paper, a 1,550 nm Intracavity structure vertical cavity surface emitting laser (VCSEL) has been designed using quaternary compound QW/barrier materials of GaInAsN/AlGaInAs matched with InP substrate. This choice has been made instead of choosing widely used GaInAsP/InP and AlGaInAs/InP to gain some advantages. In addition to the introduction of new combination in the active region, a different compound semiconductor combination AlGaAsSb/AlAsSb has been used as the DBR material for achieving lattice matching and also for achieving higher refractive index contrast. Compared to widely used GaAs/AlGaAs DBR mirror system, which needed wafer fusion with the top and bottom sides of the active region at 1,550 nm, the chosen DBR of this design is advantageous. The active material compositions have been chosen to obtain a peak gain at 1,550 nm and all other compositions have been chosen to obtain close lattice match at the same time to obtain the desired bandgap at the desired layers. The end result of this design is a VCSEL based on InP substrate which is capable of producing 1,550 nm light output and which can be constructed using widely used epitaxial techniques because all of the layers are lattice matched.     

Derivation of Lanthanide Series Crystal Field Parameters From First Principles

Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn₁₆(picHA)₁₆ series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)₃](C₃H₅N₂)₃ ⋅ 3H₂O series (Ln=Ce–Yb; dpa=2,6-dipicolinic acid) with approximate three-fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many-electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second-order parameter differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects.     

Exploring network-level performances of wireless nanonetworks utilizing gains of different types of nano-antennas with different materials

Wireless nanonetworks are not a simple extension of traditional communication networks at the nano-scale. Owing to being a completely new communication paradigm, existing research in this field is still at an embryonic stage. Furthermore, most of the existing studies focus on performance enhancement of nanonetworks via designing new channel models and routing protocols. However, the impacts of different types of nano-antennas on the network-level performances of the wireless nanonetworks remain still unexplored in the literature. Therefore, in this paper, we explore the impacts of different well-known types of antennas such as patch, dipole, and loop nano-antennas on the network-level performances of wireless nanonetworks. We also investigate the performances of nanonetworks for different types of traditional materials (e.g., copper) and for nanomaterials (e.g., carbon nanotubes and graphene). We perform rigorous simulation using our customized ns-2 simulation to evaluate the network-level performances of nanonetworks exploiting different types of nano-antennas using different materials. Our evaluation reveals a number of novel findings pertinent to finding an efficient nano-antenna from its several alternatives for enhancing network-level performances of nanonetworks. Our evaluation demonstrates that a dipole nano-antenna using copper material exhibits around 51% better throughput and about 33% better end-to-end delay compared to other alternatives for large-size nanonetworks. Furthermore, our results are expected to exhibit high impacts on the future design of wireless nanonetworks through facilitating the process of finding the suitable type of nano-antenna and suitable material for the nano-antennas.

     

Comparative analysis of refrigerant performance between LPG and R134a under subtropical climate

Journal of Thermal Analysis and Calorimetry - In this investigation, a series of experiments were conducted to explore the effects of liquefied petroleum gas (LPG) mixture of 60% propane and 40%...