Suchergebnisse

In recent decades, molecular spectroscopy has benefited from the progress of spectrometers, particularly in terms of selectivity and sensitivity, and from the continuous advancement of the analysis methods and quantum chemistry calculations. Today, rational spectroscopy is moving towards the analysis of more complex molecular systems spectrally characterized by a high density of lines. The spectral congestion of the species studied in this thesis is not only explained by low rotational constants, but also by the presence of vibrational states excited at room temperature, a high isotopic richness, a high degree of line splitting due to large amplitude motions or by a complex conformational landscape. This thesis thus illustrates various scenarios through the studies of thionyl chloride, nitrotoluenes and methoxyphenols. The rovibrational spectra of the v2 and v5 bands of the isotopologues of thionyl chloride were measured in far-infrared at the SOLEIL synchroton and analyzed using a semi-automatic approach based on evolutionary algorithms. The isomers of nitrotoluene have been targeted for military application as explosive taggants (TNT), the pure rotation spectra were measured in the microwave region in molecular jet and in the millimeter-wave region at room temperature. The millimeter-wave spectrum of 3-nitrotoluene was especially weak and congested with very large internal rotation splittings (up to several GHz) due to a very weak rotational barrier (V3=6.7659(24)cmˉ ¹). The detection limit was estimated and a linelist established. The 2-nitrotoluene and 4-nitrotoluene millimeter-wave spectra have been also partially analyzed. Finally, methoxyphenols emitted during biomass fires have also been studied as they are secondary organic aerosol precursors for their future atmospheric detection. Combined with quantum chemistry calculations, the analysis of the millimeter-wave spectrum of the 3-methoxyphenol measured at room temperature permitted the relative stability of four conformers to be determined. ; Ces ...

In recent decades, molecular spectroscopy has benefited from the progress of spectrometers, particularly in terms of selectivity and sensitivity, and from the continuous advancement of the analysis methods and quantum chemistry calculations. Today, rational spectroscopy is moving towards the analysis of more complex molecular systems spectrally characterized by a high density of lines. The spectral congestion of the species studied in this thesis is not only explained by low rotational constants, but also by the presence of vibrational states excited at room temperature, a high isotopic richness, a high degree of line splitting due to large amplitude motions or by a complex conformational landscape. This thesis thus illustrates various scenarios through the studies of thionyl chloride, nitrotoluenes and methoxyphenols. The rovibrational spectra of the v2 and v5 bands of the isotopologues of thionyl chloride were measured in far-infrared at the SOLEIL synchroton and analyzed using a semi-automatic approach based on evolutionary algorithms. The isomers of nitrotoluene have been targeted for military application as explosive taggants (TNT), the pure rotation spectra were measured in the microwave region in molecular jet and in the millimeter-wave region at room temperature. The millimeter-wave spectrum of 3-nitrotoluene was especially weak and congested with very large internal rotation splittings (up to several GHz) due to a very weak rotational barrier (V3=6.7659(24)cmˉ ¹). The detection limit was estimated and a linelist established. The 2-nitrotoluene and 4-nitrotoluene millimeter-wave spectra have been also partially analyzed. Finally, methoxyphenols emitted during biomass fires have also been studied as they are secondary organic aerosol precursors for their future atmospheric detection. Combined with quantum chemistry calculations, the analysis of the millimeter-wave spectrum of the 3-methoxyphenol measured at room temperature permitted the relative stability of four conformers to be determined. ; Ces dernières décennies, la spectroscopie moléculaire a bénéficié du progrès des spectromètres, notamment en terme de sélectivité et sensibilité, et de méthodes d'analyse et de calculs de chimie quantique toujours plus avancés. Désormais, la spectroscopie rotationnelle s'oriente vers l'analyse de systèmes moléculaires plus complexes caractérisés spectralement par une forte densité de raies. La congestion spectrale des espèces étudiées dans ma thèse s'explique non seulement par de faibles constantes rotationnelles mais aussi par la présence d'états vibrationnels excités à température ambiante, une forte richesse isotopique, un haut degré de splittings dus aux mouvements de grande amplitude ou encore par un paysage conformationnel complexe. Cette thèse illustre ainsi divers scénarii à travers les études du chlorure de thionyle, des nitrotoluènes et des méthoxyphénols. Les spectres rovibrationnels des bandes v2 et v5 des isotopologues du chlorure de thionyle ont été mesurés dans l'infrarouge lointain au synchroton SOLEIL et analysés en utilisant une approche semi-automatique basée sur des algorithmes évolutionnaires. Les isomères du nitrotoluène ont été ciblés pour leur intérêt défense comme traceurs d'explosif (TNT), les spectres de rotation pure ont été mesurés dans les régions micro-ondes en jet moléculaire et millimétrique à température ambiante. Le spectre millimétrique du 3-nitrotoluène était particulièrement faible et congestionné avec des splittings dus à la rotation interne très importants (jusqu'à plusieurs GHz) en raison d'une barrière de rotation très faible ( Vз=6.7659(24)cmˉ ¹). La limite de détection a été estimée et une liste de raies établie. Les spectres millimétriques des 2-nitrotoluène et 4-nitrotoluène ont également été partiellement analysés. Enfin, les méthoxyphénols émis lors de feux de biomasse ont également étudiés comme précurseurs d'aérosols organiques secondaires pour leur détection atmosphérique future. Associée à des calculs de chimie quantique, l'analyse du spectre millimétrique du 3-méthoxyphénol mesuré à température ambiante dans la région millimétrique a permis de déterminer la stabilité relative de quatre conformères.

AbstractNatural waters, water droplets in the air at coastal regions and wastewaters usually contain chloride ions (Cl-) in relatively high concentrations in the milimolar range. In the reactions of highly oxidizing radicals (e.g.,•OH,•NO3, or SO4•-) in the nature or during wastewater treatment in advanced oxidation processes the chloride ions easily transform to chlorine containing radicals, such as Cl•, Cl2•-, and ClO•. This transformation basically affects the degradation of organic molecules. In this review about 400 rate constants of the dichloride radical anion (Cl2•-) with about 300 organic molecules is discussed together with the reaction mechanisms. The reactions with phenols, anilines, sulfur compounds (with sulfur atom in lower oxidation state), and molecules with conjugated electron systems are suggested to take place with electron transfer mechanism. The rate constant is high (107–109M-1s-1) when the reduction potential the one-electron oxidized species/molecule couple is well below that of the Cl2•-/2Cl-couple.

"Interests, Institutions, and Defense Spending" published on by Oxford University Press.

Canada's unilateral extension of its jurisdiction over high seas fisheries in the Northwest Atlantic led in 1995 to a serious confrontation with Spain and the European Union. Although the dispute was ultimately resolved through negotiation, it raised important questions about the appropriateness and limitations of unilateral state action to protect resource and related environmental interests. This article examines the "turbot war" between Canada and Spain by analyzing the language of the disputants and outside observers to place the Canadian action in a broader normative perspective. Without trying to judge the lawfulness of the Canadian extension, it nonetheless suggests that both the conditions under which the Canadians acted and the response of the international community to the Canadian initiative provide support for a limited state right to take unilateral steps to respond to serious threats to important resources.

Contents -- INTRODUCTION: Interests, Holism, and Environmental Ethics -- ONE: A Critique of Environmental Holism -- TWO: Localizing Desire -- THREE: Biological Interests: Questioning the Mental State Theory of Welfare -- FOUR: The Principle of Inclusiveness: Establishing Priorities among Interests -- FIVE: Can Animal Rights Activists Be Environmentalists? -- SIX: Justifying the Environmentalist Agenda -- CONCLUSION: Two Dogmas of Environmental Ethics -- References -- Index -- A -- B -- C -- D -- E -- F -- G -- H -- I -- J -- K -- L -- M -- N -- O -- P -- R -- S -- T -- U -- V -- W

"France is the only European ally -- except for the United Kingdom (UK) -- that regards its military capabilities, operational performance, and defense industry as vital levers to exert global influence. While the French believe strongly in their need to preserve "strategic independence," they see new challenges in the evolving international security environment that will oblige them to accept greater cooperation with others, even in areas once considered too sensitive to discuss. Although some French strategists remain uncomfortable with the notion of closer defense ties with the United States, others ask whether there might be a greater danger ahead: specifically, if Europe's strength dissipates as America "rebalances" toward the Asia-Pacific region, where does France turn to find capable and willing partners to protect its security interests? The Libyan conflict in 2011 brought to light many of the cross-currents that are shaping French defense policy. French leaders are proud of their military's performance in Libya, which many view as having validated President Nicolas Sarkozy's decision in early 2009 on France's return to full participation in North Atlantic Treaty Organization (NATO) military structures. But the conflict also exposed Europe's continuing dependence on U.S. military capabilities, reinforced France's lack of confidence in Germany and the European Union as serious military partners, and increased its determination to improve defense cooperation with the United Kingdom. Despite some downsizing, France has resisted the dramatic cuts in defense spending and capabilities under way elsewhere in Europe. If Sarkozy wins the presidential election on May 6, 2012, he can be expected to continue many elements of the transformation strategy launched by his government's June 2008 White Book on Defense and National Security. If the Socialist Party challenger, Francois Hollande, wins, he will reassure leaders at the NATO Summit in Chicago (May 20-21, 2012) that France will maintain its nuclear deterrent and participation in NATO military structures. But reductions in the defense budget are likely whether Sarkozy or Hollande wins. There will be opportunities for expanded U.S.-French and perhaps U.S.-UK-French defense cooperation under a Sarkozy or Hollande administration. But Paris and Washington will need to manage tensions related to their respective defense industries. For the United States, more is at stake than the health of the French defense establishment. France's policies, capabilities, and operational commitments can play an important role in shaping those of many other Europeans. By working even more closely with its oldest ally, the United States can help ensure the credibility and effectiveness of the Alliance as a whole."--P. 1-2. ; "April 2012." ; Includes bibliographical references (p. 31-35). ; Executive summary -- Changing strategic context : view from Paris -- French defense capabilities : major trends -- France and NATO : coming to terms -- Libya : a wake-up call -- In search of capable and reliable European partners -- French-British defense cooperation : a new route to European defense -- Impact of French elections -- The United States and "la grande nation" -- A cautionary note. ; "France is the only European ally -- except for the United Kingdom (UK) -- that regards its military capabilities, operational performance, and defense industry as vital levers to exert global influence. While the French believe strongly in their need to preserve "strategic independence," they see new challenges in the evolving international security environment that will oblige them to accept greater cooperation with others, even in areas once considered too sensitive to discuss. Although some French strategists remain uncomfortable with the notion of closer defense ties with the United States, others ask whether there might be a greater danger ahead: specifically, if Europe's strength dissipates as America "rebalances" toward the Asia-Pacific region, where does France turn to find capable and willing partners to protect its security interests? The Libyan conflict in 2011 brought to light many of the cross-currents that are shaping French defense policy. French leaders are proud of their military's performance in Libya, which many view as having validated President Nicolas Sarkozy's decision in early 2009 on France's return to full participation in North Atlantic Treaty Organization (NATO) military structures. But the conflict also exposed Europe's continuing dependence on U.S. military capabilities, reinforced France's lack of confidence in Germany and the European Union as serious military partners, and increased its determination to improve defense cooperation with the United Kingdom. Despite some downsizing, France has resisted the dramatic cuts in defense spending and capabilities under way elsewhere in Europe. If Sarkozy wins the presidential election on May 6, 2012, he can be expected to continue many elements of the transformation strategy launched by his government's June 2008 White Book on Defense and National Security. If the Socialist Party challenger, Francois Hollande, wins, he will reassure leaders at the NATO Summit in Chicago (May 20-21, 2012) that France will maintain its nuclear deterrent and participation in NATO military structures. But reductions in the defense budget are likely whether Sarkozy or Hollande wins. There will be opportunities for expanded U.S.-French and perhaps U.S.-UK-French defense cooperation under a Sarkozy or Hollande administration. But Paris and Washington will need to manage tensions related to their respective defense industries. For the United States, more is at stake than the health of the French defense establishment. France's policies, capabilities, and operational commitments can play an important role in shaping those of many other Europeans. By working even more closely with its oldest ally, the United States can help ensure the credibility and effectiveness of the Alliance as a whole."--P. 1-2. ; Mode of access: Internet.