Search results for "Crossing point"
showing 4 items of 4 documents
Understanding the reactivity of transition metal complexes involving multiple spin states
2003
International audience; In coordination chemistry, many reactions involve several electronic states, in particular states of different spin. This phenomenon of ‘Multiple-State Reactivity’ has been recognized for some time, both for gas-phase reactions of ‘bare’ metal ions, and for transition metal complexes in solution. Until recently, however, much of the discussion of these systems has remained qualitative, because standard computational methods do not allow the location of the critical points for these processes, the Minimum Energy Crossing Points (MECPs) between states of different spin. Increased computational resources and new algorithms now enable MECPs to be located for large, reali…
La stima del crossing-point nel modello di Cox per l'analisi di sopravvivenza: una proposta
2008
La variazione dell'effetto di un fattore di rischio in un modello di sopravvivenza a rischi proporzionali di Cox è di particolare interesse in molte applicazioni, in quanto l'allontanamento dall'ipotesi di proporzionalità dei rischi rende il modello inadeguato. Di particolare interesse è il caso in cui le funzioni di rischio di due gruppi si intersecano, ovvero, più in generale, il coefficiente di regressione cambia segno dopo un istante temporale detto crossing-point. In questo lavoro si propone una procedura per la stima del crossing-point applicabile anche al caso di variabili quantitative, e si discutono tre diversi metodi per la corrispondente stima intervallare. L'approccio è illustra…
A flexible approach to the crossing hazards problem
2010
We propose a simple and flexible framework for the crossing hazards problem. The method is not confined to two-sample problems, but may also work with continuous exposure variables whose effect changes its sign at some time-point of the observed follow-up time. Penalized partial likelihood estimation relies upon the assumption of a smooth hazard ratio via low-rank basis splines with a conventional difference penalty to ensure smoothness, and additional ad hoc penalties to obtain restricted estimates useful in the context of crossing hazards. The framework naturally also leads to a statistical test that has good power for revealing a global effect under several alternatives, including crossi…
la prospection systématique d’un fond de rivière : l’exemple du Doubs
2020
La présentation des méthodes mises en œuvre et des résultats obtenus à l’occasion d’une opération de prospection subaquatique systématique menée sur la rivière Doubs, en amont de Verdun-sur-le-Doubs (Saône-et-Loire), illustre en grandeur réelle l’intérêt de la démarche adoptée, fondée sur des principes simples, dans la perspective d’un inventaire systématique du patrimoine fluvial immergé. La diversité des vestiges découverts et leur répartition sur la longue durée en soulignent la pertinence mais également, s’il en était encore besoin, la réalité du formidable potentiel archéologique que recèlent les cours d’eau. The presentation of the methods used and results obtained during a systematic…