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Matrix Isolation Studies of Photochemical and Thermal Reactions of Cyclic Organic Substrates with Chromyl Chloride and Ozone/O AtomsHoops, Michael Dean 25 August 2008 (has links)
No description available.
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Spectroscopic identification of complex species containing water and ammonia and their importance to icy outer solar system bodiesEnnis, Courtney January 2009 (has links)
[Truncated abstract] This thesis examines the bonding interactions and chemical processes associated with irradiated water (H2O) and ammonia (NH3) molecules. The experiments conducted in the present study are designed to replicate the surface chemistry of outer Solar System bodies, particularly the icy surfaces of Saturn's inner moons. Infrared (IR) spectroscopy is used to identify the H2ONH3 complex isolated in an argon (Ar) matrix. An electric discharge is then applied to the H2O and NH3 species to produce the hydroxyl-ammonia (OHNH3) complex and the water-amidogen (H2ONH2) complex. Finally, the ammonia-oxygen (NH3O2) complex is formed in an Ar matrix, complementing previous studies performed by the Quickenden research group, which investigated the conversion of OH radicals into molecular O2 on icy planetary surfaces. ... An electric discharge is applied to the NH3 in Ar mixture, producing the NH2 radical subunit of the complex. Two absorption bands are assigned to the H2O subunit vibrational frequencies of the complex; at 1616.1 cm-1 for the ¿2 HOH bending fundamental and at 3532.1 cm-1 for the ¿1 OH bonded stretching fundamental. Two absorption bands are also assigned to the NH2 radical subunit vibrational frequencies of the complex; at 1498.5 cm-1 for the ¿2 HNH bending fundamental and at 3260.8 cm-1 for the ¿3 NH asymmetric stretching fundamental. These assignments are verified by the isotope substitution method, involving the formation of the deuterated D2OND2 complex analogue in an Ar matrix and the measurement of the isotope induced shifts in peak position in the IR region. The isotopic shifts displayed by the IR absorption bands are in good agreement with the theoretically calculated shifts in vibration frequency when going from the H2ONH2 complex fundamentals to the D2OND2 complex fundamentals. The theoretical calculations also derived an interaction energy of 5.2 kcal mol-1 for the HOHNH2 structure of the H2ONH2 complex. This HOHNH2 structure is also confirmed as the preferred structure of the H2ONH2 complex in the IR experiments, by the observation of a large shift in position of the absorption band associated with the H2O subunit ¿1 OH stretching fundamental, away from the position of the H2O monomer ¿1 OH stretching fundamental. This indicates that the H2O subunit donates a hydrogen for the complex bond in the HOHNH2 complex. The NH3O2 complex is identified in solid Ar matrices at 10.5 K by IR analysis. The NH3O2 complex is formed by the co-deposition of gaseous NH3 in Ar mixtures with O2 in Ar gas mixtures. An absorption band is assigned to the ¿1 OO stretching fundamental for the O2 subunit of the NH3O2 complex at 1552.0 cm-1. This assignment is verified by the isotope substitution method, involving the formation of the deuterated ND3O2 complex analogue in an Ar matrix and the measurement of the isotope induced shift in peak position in the IR region. The isotopic shift displayed by the IR absorption band is in good agreement with the theoretically calculated shift in vibration frequency when going from the NH3O2 complex fundamental to the ND3O2 complex fundamental. The theoretical calculations also derived an interaction energy of 0.28 kcal mol-1 for the NH3O2 complex.
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Dynamics and Photodynamics of Acetylacetone in para-Hydrogen matricesLozada-Garcia, Rolando 12 December 2012 (has links) (PDF)
Acetylacetone (AcAc) exists as a mixture of enol and keto tautomers. Besides providing a good example for the study of tautomerization, it is a model system for investigating intramolecular hydrogen bonds in its enol form. Trapping AcAc in the soft para-Hydrogen (pH2 ) environment brings out new opportunities to investigate its properties. Infrared spectra of the samples give a good characterization of the two stable enol and keto tautomers. The keto/enol ratio in solid pH2 is found to be higher than in other matrices. While vibrational bands of keto are narrow, those of enol are broad, reflecting the intrinsic properties of the enol which exhibits three entangled large amplitude motions (two methyl torsions and the intramolecular hydrogen transfer). Surprisingly, narrowing of some of these bands is observed in a slow time evolution. This effect is interpreted as a consequence of nuclear spin conversion in the hydrogen atoms of the methyl groups, giving access to AcAc species differing by their nuclear spin symmetry. This offers new pertinent investigations on the large amplitude motions, especially on the intramolecular hydrogen transfer. AcAc/pH2 samples have been irradiated by UV laser beams. Irradiation at 266 nm induces isomerization from the stable chelated enol form to non chelated conformers, similarly to the case of other matrices. A clear IR signature of the conformers is obtained thanks to the pH2 host. Irradiation at 248 nm induces the enol/keto tautomerization. The kinetics of this interconversion highlights a non-direct process. Fragmentation is clearly observed under irradiation at 193 nm, followed by chemical reaction with the hydrogen host.
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Understanding the Factors That Control Increased Photo-reactivity and Selectivity Of Vinylic And Aromatic AzidesOsisioma, Onyinye 22 October 2020 (has links)
No description available.
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Reaction Mechanism and Detection of Elusive C, N, and O Centered Radicals and Intermediates in Solution and Solid StateSarkar, Sujan K. January 2015 (has links)
No description available.
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Dynamics and Photodynamics of Acetylacetone in para-Hydrogen matrices / Dynamique and Photodynamique de l' Acetylacetone en matrice de para-HydrogeneLozada-Garcia, Rolando 12 December 2012 (has links)
L’acétylacétone (AcAc) existe sous deux formes tautomères, énol et kéto. Sous sa forme énol chélaté, c’est une des molécules les plus simples présentant une liaison hydrogène intramoléculaire. Nous l’avons isolée dans la matrice « quantique » de parahydrogène (pH2) pour étudier ses propriétés en bénéficiant des avantages spécifiques de ce solide cryogénique. Les spectres infrarouges apportent une caractérisation claire des formes énol et kéto. Le rapport kéto/énol est plus important en matrice de pH2 que dans les autres matrices. Les bandes du kéto sont fines alors que certaines bandes de l’énol sont très larges à cause de la présence de la liaison hydrogène. Plusieurs bandes s’affinent très lentement avec le temps. Cet effet surprenant a été interprété en terme de conversion nucléaire de spin dans un groupement méthyle d’AcAc, donnant accès aux spectres de niveaux de torsion différents. Les résultats offrent alors un nouveau moyen d’investigation des mouvements de grande amplitude de la molécule (mouvements couplés de torsion des méthyles et du transfert d’hydrogène interne). La photolyse UV des matrices AcAc/pH2 a été étudiée. Une irradiation à 266 nm conduit à l’isomérisation de l’énol sous différentes formes non chélatées ; des spectres très bien résolus de ces formes sont obtenus grâce aux propriétés du pH2 solide. En irradiant à 248 nm, on observe la tautomérisation vers la forme kéto, l’étude cinétique démontrant que le processus n’est pas direct à partir de l’énol chélaté. Enfin, une irradiation à 193 nm provoque la fragmentation de la molécule, processus qui peut être suivi de réactions avec l’hydrogène de la matrice. / Acetylacetone (AcAc) exists as a mixture of enol and keto tautomers. Besides providing a good example for the study of tautomerization, it is a model system for investigating intramolecular hydrogen bonds in its enol form. Trapping AcAc in the soft para-Hydrogen (pH2 ) environment brings out new opportunities to investigate its properties. Infrared spectra of the samples give a good characterization of the two stable enol and keto tautomers. The keto/enol ratio in solid pH2 is found to be higher than in other matrices. While vibrational bands of keto are narrow, those of enol are broad, reflecting the intrinsic properties of the enol which exhibits three entangled large amplitude motions (two methyl torsions and the intramolecular hydrogen transfer). Surprisingly, narrowing of some of these bands is observed in a slow time evolution. This effect is interpreted as a consequence of nuclear spin conversion in the hydrogen atoms of the methyl groups, giving access to AcAc species differing by their nuclear spin symmetry. This offers new pertinent investigations on the large amplitude motions, especially on the intramolecular hydrogen transfer. AcAc/pH2 samples have been irradiated by UV laser beams. Irradiation at 266 nm induces isomerization from the stable chelated enol form to non chelated conformers, similarly to the case of other matrices. A clear IR signature of the conformers is obtained thanks to the pH2 host. Irradiation at 248 nm induces the enol/keto tautomerization. The kinetics of this interconversion highlights a non-direct process. Fragmentation is clearly observed under irradiation at 193 nm, followed by chemical reaction with the hydrogen host.
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Signatures spectroscopiques et propriétés thermochimiques de petits complexes hydratés par des approches expérimentales et théoriques / Spectroscopic signatures and thermochemical properties of small hydrated complexes by experimental and theoretical approachesDargent, Damien 24 September 2015 (has links)
La formation des liaisons non covalentes et plus particulièrement des liaisons hydrogène joue un rôle majeur dans de nombreux processus biologiques, atmosphériques et astrophysiques. Les complexes hydratés (1:n) entre une molécule de diacétyle (C4H6O2) et une à plusieurs molécules d’eau (H2O) ont été étudiés selon des approches théoriques et expérimentales dans le but de caractériser leur structure et leur spectre vibrationnel. Sur le plan théorique les propriétés énergétiques, géométriques et vibrationnelles des complexes C4H6O2:(H2O)n ont été déterminées et une étude topologique spécifique a été réalisée sur le complexe 1:1 C4H6O2:H2O. A travers cette étude théorique, les premières étapes du mécanisme d’hydratation du diacétyle ont été mises en évidence et analysées en détail. En s’appuyant sur les techniques spectroscopiques infrarouges d’isolation en matrice de néon et de jet supersonique, plusieurs modes de vibration des isomères du complexe 1:1 ont été identifiés et leurs fréquences déterminées Enfin, un jeu de constantes de couplage anharmonique a été obtenu à partir de l’analyse des bandes harmoniques et de combinaison. / The formation of non-covalent bonds and more particularly hydrogen bonds play a major role in several biological, atmospheric and astrophysical chemistry issues. The theoretical and experimental investigation of hydrated complexes (1:n) between a diacetyl molecule (C4H6O2) and one or several water molecules (H2O) have been studied to characterize their structure and their vibrational spectrum. Energetical, geometrical and vibrational properties of C4H6O2:(H2O)n complexes have been determined from ab initio and DFT calculations. Moreover a topological analysis of the 1:1 C4H6O2:H2O complex has been carried out. Such theoretical investigations enabled to evidence and analyze in detail the first steps of diacetyl hydration. From neon matrix isolation and supersonic jet techniques coupled to infrared spectroscopy, several vibrational modes of 1:1 isomers have been detected and therefore their frequencies have been determined. Finally a set of anharmonic coupling constants have been derived from the spectral analysis of harmonic and combination bands.
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Crosslinking of polyaniline with aryl azides and the photolysis of vinyl azides and azidopropanonesJadhav, Abhijit V. 22 April 2008 (has links)
No description available.
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