Search results for "functional"
showing 10 items of 4822 documents
First Principles Calculations for Hydrogenation of Acrolein on Pd and Pt: Chemoselectivity Depends on Steric Effects on the Surface
2016
The chemoselective hydrogenation of acrolein on Pt(111) and Pd(111) surfaces is investigated employing density functional theory calculations. The computed potential energy surfaces together with the analysis of reaction mechanisms demonstrate that steric effects are an important factor that governs chemoselectivity. The reactions at the C=O functionality require more space than the reactions at the C=C functionality. Therefore the formation of allyl alcohol is more favorable at low coverage, while the reduction of the C=C bond and the formation of propanal becomes kinetically more favorable at higher coverage. The elementary reaction steps are found to follow different reaction mechanisms,…
Steric vs. electronic stereocontrol in syndio- or iso-selective ROP of functional chiral β-lactones mediated by achiral yttrium-bisphenolate complexes
2018
International audience; Origins of stereoselectivity in ROP of racemic chiral cyclic esters promoted by achiral yttrium complexes, resulting in the formation of highly heterotactic polylactide, and highly syndiotactic or, more uniquely, highly isotactic poly(3-hydroxybutyrate)s, are discussed. A close interplay between the nature of the cyclic ester, most particularly of the exocyclic functional chain installed on the chiral center of β-lactones, and the ortho-substituents installed on the phenolate rings of the ligand, results in various determining secondary interactions of steric and also electronic nature.
A Computational Study of Ethylene C−H Bond Activation by [Cp*Ir(PR3)]
2001
It has previously been demonstrated that both [(C5Me5)Ir(PMe3)(CH=CH2)H] and [(C5Me5)Ir(PMe3)(H2C=CH2)] are formed when [(C5Me5)Ir(PMe3)] is thermolytically generated in the presence of ethylene. At higher temperatures, the vinyl hydride is converted to the eta2-ethylene adduct. Density functional theory has now been used to investigate this reaction, using the B3LYP functional, two types of basis sets (LanL2DZ and TZV*), and two models of the [(C5R5)Ir(PR3)] species (R=H and CH3). The study consists of full optimizations of local minima, first-order saddle points, and minimum energy crossing points (MECP). The experimental results are best accounted for by considering both singlet and trip…
Substituent effects in trans-p,p'-disubstituted azobenzenes: X-ray structures at 100 K and DFT-calculated structures.
2014
The crystal and molecular structures of twopara-substituted azobenzenes with π-electron-donating –NEt2and π-electron-withdrawing –COOEt groups are reported, along with the effects of the substituents on the aromaticity of the benzene ring. The deformation of the aromatic ring around the –NEt2group inN,N,N′,N′-tetraethyl-4,4′-(diazenediyl)dianiline, C20H28N4, (I), may be caused by steric hindrance and the π-electron-donating effects of the amine group. In this structure, one of the amine N atoms demonstrates clearsp2-hybridization and the other is slightly shifted from the plane of the surrounding atoms. The molecule of the second azobenzene, diethyl 4,4′-(diazenediyl)dibenzoate, C18H18N2O4,…
An investigation of the neural circuits underlying reaching and reach-to-grasp movements: from planning to execution
2014
Experimental evidence suggests the existence of a sophisticated brain circuit specifically dedicated to reach-to-grasp planning and execution, both in human and non-human primates (Castiello, 2005). Studies accomplished by means of neuroimaging techniques suggest the hypothesis of a dichotomy between a "reach-to-grasp" circuit, involving the anterior intraparietal area, the dorsal and ventral premotor cortices (PMd and PMv - Castiello and Begliomini, 2008; Filimon, 2010) and a "reaching" circuit involving the medial intraparietal area and the superior parieto-occipital cortex (Culham et al., 2006). However, the time course characterizing the involvement of these regions during the planning …
Stochastic algorithms for robust statistics in high dimension
2016
This thesis focus on stochastic algorithms in high dimension as well as their application in robust statistics. In what follows, the expression high dimension may be used when the the size of the studied sample is large or when the variables we consider take values in high dimensional spaces (not necessarily finite). In order to analyze these kind of data, it can be interesting to consider algorithms which are fast, which do not need to store all the data, and which allow to update easily the estimates. In large sample of high dimensional data, outliers detection is often complicated. Nevertheless, these outliers, even if they are not many, can strongly disturb simple indicators like the me…
THE ROLE OF UNBOUNDED TIME-SCALES IN GENERATING LONG-RANGE MEMORY IN ADDITIVE MARKOVIAN PROCESSES
2013
Any additive stationary and continuous Markovian process described by a Fokker–Planck equation can also be described in terms of a Schrödinger equation with an appropriate quantum potential. By using such analogy, it has been proved that a power-law correlated stationary Markovian process can stem from a quantum potential that (i) shows an x-2 decay for large x values and (ii) whose eigenvalue spectrum admits a null eigenvalue and a continuum part of positive eigenvalues attached to it. In this paper we show that such two features are both necessary. Specifically, we show that a potential with tails decaying like x-μ with μ < 2 gives rise to a stationary Markovian process which is not p…
Narrow Bound States of the DNN System
2012
We report on a recent calculation of the properties of the $DNN$ system, a charmed meson with two nucleons. The system is analogous to the $\bar K NN$ system substituting a strange quark by a charm quark. Two different methods are used to evaluate the binding and width, the Fixed Center approximation to the Faddeev equations and a variational calculation. In both methods we find that the system is bound by about 200 MeV and the width is smaller than 40 MeV, a situation opposite to the one of the $\bar K NN$ system and which makes this state well suited for experimental observation.
The Love of Money and Pay Level Satisfaction: Measurement and Functional Equivalence in 29 Geopolitical Entities around the World
2006
Demonstrating the equivalence of constructs is a key requirement for cross-cultural empirical research. The major purpose of this paper is to demonstrate how to assess measurement and functional equivalence or invariance using the 9-item, 3-factor Love of Money Scale (LOMS, a second-order factor model) and the 4-item, 1-factor Pay Level Satisfaction Scale (PLSS, a first-order factor model) across 29 samples in six continents (N = 5973). In step 1, we tested the configural, metric and scalar invariance of the LOMS and 17 samples achieved measurement invariance. In step 2, we applied the same procedures to the PLSS and nine samples achieved measurement invariance. Five samples (Brazil, China,…
Agro-food markets’ functional efficiency, products’ quality and information’s role
2018
Nowadays agro-food productions’ quality and markets’ economic efficiency are strictly connected and related to the increasing information’s role that is no doubt simplify by the global presence of the World Wide Web system. It is possible to assert that this kind of situation does not always safeguard information’s safety and propriety and at the same time consumers’ aware and complete choice capability. From a production markets’ economic efficiency point of view these elements contribute to create some kind of functional distortions able to prevent their proper working system under the economic theory profile and supply misunderstandings and informational asymmetries. These specific condi…