Improvements in DFT Calculations of Spin–Spin Coupling Constants

Different types of spin–spin coupling constants (SSCCs) for several representative small molecules are evaluated and analyzed using a combination of 10 exchange functionals with 12 correlation functionals. For comparison, calculations performed using MCSCF, SOPPA, other common DFT methods, and also experimental data are considered. A detailed study of the percentage of Hartree–Fock exchange energy in SSCCs and in its four contributions is carried out. From the above analysis, a combined functional formed with local Slater (34%), Hartree–Fock exchange (66%), and P86 correlation functional (S66P86) is proposed in this paper. The accuracy of the values obtained with this hybrid functional (mean absolute deviation of 4.5 Hz) is similar to that of the SOPPA method (mean absolute deviation of 4.6 Hz).

Magnetic nanoparticles supported oxime palladacycle as a highly efficient and separable catalyst for room temperature Suzuki–Miyaura coupling reaction in aqueous media

A novel magnetic nanoparticle-supported oxime palladacycle catalyst was successfully prepared and characterized. The magnetically recoverable catalyst was evaluated in the room temperature Suzuki–Miyaura cross-coupling reaction of aryl iodides and bromides in aqueous media. The catalyst was shown to be highly active under phosphine-free and low Pd loading (0.3 mol%) conditions. The catalyst could be easily separated from the reaction mixture using an external magnet and reused for six consecutive runs without significant loss of activity.

Intramolecular surfaces for vicinal proton–proton coupling constants 3JHH

Equations for the intramolecular surfaces of the 3JHH coupling constants in ethane, ethylene, and acetylene are formulated, and the corresponding coefficients are estimated from calculations at the DFT/B3LYP level. The chosen variables are changes in bond lengths, in the torsion angle φ between the coupled protons Ha and Hb, in bond angles, and in dihedral angles. The 3JHH surface of ethane is formulated as an extended Karplus equation with the coefficients of a truncated Fourier series on the torsion angle φ expanded as second-order Taylor series in the chosen variables taking into account the invariance of 3JHH under reflections and rotations of nuclear coordinates. Partial vibrational contributions from linear and square terms corresponding to changes in the geometry of the Ha − Ca − Cb − Hb fragment are important while those from cross terms are small with a few exceptions. The 3JHH surface of ethane is useful to predict contributions to 3JHH from changes in local geometry of derivatives but vibrational contributions are predicted less satisfactorily. The predicted values at the B3LYP/BS2 level of the 3JHH couplings (vibrational contributions at 300 K) from equilibrium geometries are 9.79 (−0.17) for acetylene, and 17.08 (1.93) and 10.73(0.93) for the trans and cis couplings of ethylene.

Cross-dehydrogenative coupling reaction using copper oxide impregnated on magnetite in deep eutectic solvents

The synthesis of different tetrahydroisoquinolines using choline chloride : ethylene glycol as a deep eutectic solvent (DES) and copper(II) oxide impregnated on magnetite as a catalyst has been accomplished successfully. The copper catalyst amount is the lowest loading ever reported. The presence of DES showed to be essential since the reaction in the absence of this medium did not proceed. A direct proportional relationship was found between the conductivity of DES medium and the yield obtained. The DES and the catalyst could be reused up to ten times without any detrimental effect on the yield of the reaction, with the aerobic conditions making the protocol highly sustainable, where the only waste is water.

The syntheses and characterization of nickel complexes; investigation of Ni(dppp)2 and [NiX(dppp)n]x, potentially catalytically active nickel(0)/(I) species for cross-coupling reactions

This thesis describes an investigation in which we compare Ni(0), Ni(I) and Ni(II) complexes containing 1,3-bis(diphenylphosphino)propane (dppp) as a phosphine ligand for their abilities to effect three types of cross-coupling reactions: Buchwald-Hartwig Amination, Heck-Mizoroki, and Suzuki-Miyaura cross-coupling reactions with different types of substrates. The Ni(0) complex Ni(dppp)2 is known and we have synthesized it via a new procedure involving zinc reduction of the known NiCl2(dppp) in the presence of an excess of dppp. The Ni(0) complex was characterized by NMR spectroscopy and X-ray crystallography. Since Ni(I) complexes of dppp seem unknown, we have synthesized what at this stage appear to be NiXdpppn/[NiX(dppp)n]x (X = Cl, Br, I; n = 1,2, x = 1, 2) by comproportionation of molar equivalents of Ni(dppp)2 and NiX2dppp, X= Cl, Br, I.

BIDIRECTIONAL AC-DC CONVERTERS USING ONE CYCLE CONTROL (OCC) FOR ELECTRIC VEHICLES

The electric vehicle (EV) market has seen a rapid growth in the recent past. With an increase in the number of electric vehicles on road, there is an increase in the number of high capacity battery banks interfacing the grid. The battery bank of an EV, besides being the fuel tank, is also a huge energy storage unit. Presently, it is used only when the vehicle is being driven and remains idle for rest of the time, rendering it underutilized. Whereas on the other hand, there is a need of large energy storage units in the grid to filter out the fluctuations of supply and demand during a day. EVs can help bridge this gap. The EV battery bank can be used to store the excess energy from the grid to vehicle (G2V) or supply stored energy from the vehicle to grid (V2G ), when required. To let power flow happen, in both directions, a bidirectional AC-DC converter is required. This thesis concentrates on the bidirectional AC-DC converters which have a control on power flow in all four quadrants for the application of EV battery interfacing with the grid. This thesis presents a bidirectional interleaved full bridge converter topology. This helps in increasing the power processing and current handling capability of the converter which makes it suitable for the purpose of EVs. Further, the benefit of using the interleaved topology is that it increases the power density of the converter. This ensures optimization of space usage with the same power handling capacity. The proposed interleaved converter consists of two full bridges. The corresponding gate pulses of each switch, in one cell, are phase shifted by 180 degrees from those of the other cell. The proposed converter control is based on the one-cycle controller. To meet the challenge of new requirements of reactive power handling capabilities for grid connected converters, posed by the utilities, the controller is modified to make it suitable to process the reactive power. A fictitious current derived from the grid voltage is introduced in the controller, which controls the converter performance. The current references are generated using the second order generalized integrators (SOGI) and phase locked loop (PLL). A digital implementation of the proposed control ii scheme is developed and implemented using DSP hardware. The simulated and experimental results, based on the converter topology and control technique discussed here, are presented to show the performance of the proposed theory.

Misurazione della Sostenibilità in Azienda. Approccio Quantitativo all'Analisi della Letteratura attraverso Bibliografic Coupling.

L'elaborato si impegna ad esporre i risultati derivanti da una revisione estensiva della letteratura riguardante le pratiche di misurazione della sostenibilità in azienda. Si è scelto un approccio al problema di impostazione bibliometrico, consistente in analisi statistiche di dati bibliografici ricavabili osservando le relazioni tra documenti. Si sono utilizzati strumenti di clustering per categorizzare la letteratura ed individuare le aree di maggior interesse potenziali per aziende che desiderino investire con successo nella sostenibilità. Come risultato, si è ottenuta una chiara identificazione delle principali tematiche che devono essere tenute in considerazione nell’affrontare valutazioni relative alla misurazione e valorizzazione dei concetti di sostenibilità e impatto ambientale in ambito aziendale. Il presente lavoro si presenta inoltre come guida metodologica per un approccio quantitativo alla revisione della letteratura, adattabile ed applicabile in maniera iterativa per un continuo monitoraggio del tema o per indagini in altri ambiti. Questa tesi si pone dunque come base per ricerche e analisi successive finalizzate alla comprensione della letteratura.

Gradient-Domain Bidirectional Path Tracing

Gradient-domain path tracing has recently been introduced as an efficient realistic image synthesis algorithm. This paper introduces a bidirectional gradient-domain sampler that outperforms traditional bidirectional path tracing often by a factor of two to five in terms of squared error at equal render time. It also improves over unidirectional gradient-domain path tracing in challenging visibility conditions, similarly as conventional bidirectional path tracing improves over its unidirectional counterpart. Our algorithm leverages a novel multiple importance sampling technique and an efficient implementation of a high-quality shift mapping suitable for bidirectional path tracing. We demonstrate the versatility of our approach in several challenging light transport scenarios.

M-AARE - Coupling atmospheric, hydrological, hydrodynamic and damage models in the Aare river basin, Switzerland

The triggering mechanism and the temporal evolution of large flood events, especially of worst-case scenarios, are not yet fully understood. Consequently, the cumulative losses of extreme floods are unknown. To study the link between weather conditions, discharges and flood losses it is necessary to couple atmospheric, hydrological, hydrodynamic and damage models. The objective of the M-AARE project is to test the potentials and opportunities of a model chain that relates atmospheric conditions to flood losses or risks. The M-AARE model chain is a set of coupled models consisting of four main components: the precipitation module, the hydrology module, the hydrodynamic module, and the damage module. The models are coupled in a cascading framework with harmonized time-steps. First exploratory applications show that the one way coupling of the WRF-PREVAH-BASEMENT models has been achieved and provides promising new insights for a better understanding of key aspects in flood risk analysis.

The coupling and mutual impedance between balanced wire-arm conical log-spiral antennas /

Includes bibliographical references (76-77)

Distributed coupling to surface wave antennas /

Includes bibliographical references.

Coupling of antenna elements to a circular surface waveguide /

"Contract No. AF33(616)-310 RDO No. R-112-110 SR-6f2"

The electrical admittance of a homogeneous polarized fully electroded circular disc, loss-less and mechanically free : analysis, including Rayleigh correction, data for routine determination of elastic modulus and Piezoelectric coupling, and discussion of limitation of correction, anisotrophy parameters involved, and deductions concerning dimensional standarization /

"ONR Contract No. Nonr-1055(00)."

Vibration and dissociation coupling behind strong shock waves. Paper presented at the Symposium on Dynamics of Manned Lifting Planetary Entry,

Cover title.