Refine
Year of publication
Document Type
- Article (24)
- Postprint (3)
- Other (1)
- Part of Periodical (1)
Is part of the Bibliography
- yes (29)
Keywords
- photochemistry (3)
- charge-transfer (2)
- dynamics (2)
- electronic-structure (2)
- iron (2)
- spectra (2)
- Energy (1)
- FE (1)
- Ligands (1)
- Metals (1)
Competitive resonance at the carbonyl group as visualized by the natural bond orbital analysis
(1997)
In this work we present theoretical studies of the hydrolytic reaction of methyl formate, formamide and urea with one water molecule. The studied systems contain two additional water molecules which can act as bifunctional acid- base catalysts. These water molecules catalyze proton transfers between the primary reacting species. Our models describe the concerted transfer of two protons in every reaction step. The calculations have been carried out with the Becke3LYP/6-31G* method. Unspecific solvation effects have been included by means of a polarizable continuum model. Substrate reactivity differences as well as preferences for different reaction pathways can be discussed with the aid of these molecular systems. The studied alternative mechanisms include the common addition-elimination mechanism via a tetrahedral intermediate, and a concerted SN-like mechanism without a reaction intermediate. Our results suggest that the proved decreasing substrate reactivity in the order ester, amide, urea is caused by a rising resonance stabilization of the reaction centre, and not by a different positive partial charge of the carbonyl carbon. It is also concluded, that the probability of a concerted addition of a nucleophile and elimination of a leaving group without a tetrahedral intermediate rises in the order ester, amide, urea. The ordering of reactivity is not influenced by this behaviour.
Basicities of 16 acyl compounds including selected aldehydes, ketones, esters, amides and ureas in the gas phase and in water were calculated with the Becke3LYP/6-31G* method. Solvent effects were modeled using a polarizable electrostatic continuum representation of the solvent. The properties of the electron densities of protonated molecules were described by localized bond orbitals. Our results suggest that the carbonyl oxygen is the preferred site of protonation for all molecules studied. Calculated pKa values in water range from -12 for aldehydes to + 1.5 for ureas. They agree well with published experimental data. We found that a high basicity of acyl compounds at the carbonyl oxygen is coupled with a large amount of additional resonance stabilization at the carbonyl group. The protonation of the leaving group of eaters, amides and ureas is less preferred, but the basicity difference between C=O and -OR or -NR2 decreases from esters to ureas. Calculated pKa values for this site range from -18 for esters to + 3 for ureas. These values are often not accessible by experiment. The structure of carboxylic acid derivatives protonated at the leaving group is determined by prefragmentation of the molecules into an acylium ion or positively charged isocyanate and an alcohol or amine. (C) 1998 Elsevier Science B.V.
Investigation on the photoreactions of Nitrate and Nitrite ions with selected Azaarenes in water
(1999)
Portal alumni
(2012)
Das zurückliegende Jahr stand an der Universität Potsdam auch im Zeichen des zwanzigjährigen Jubiläums der Hochschule. Am 15. Juli 1991, wurde sie gegründet und während einer Festwoche feierten Professorinnen und Professoren, Mitarbeiterinnen, Mitarbeiter und Studierende dieses Jubiläum gebührend. Seit der Gründung der größten brandenburgischen Hochschule sind wissenschaftliches Renommee, Ansehen und Attraktivität stetig gewachsen. Gerade in den letzten Jahren hat sie ihr Profil geschärft. Vor allem die Kognitions-, die Geo- und Biowissenschaften sind hier zu nennen. Aber auch die Lehrerbildung besitzt einen hohen Stellenwert. International anerkannte Forschungsbereiche, Wissenschaftspreise, eine erfolgreiche Drittmittelbilanz und nicht zuletzt die bauliche Entwicklung an allen drei Standorten sind sichtbare Indikatoren für die erfolgreiche Entwicklung, die die Universität Potsdam in den letzten zwei Jahrzehnten durchlaufen hat. Die drei ehemaligen Präsidenten sowie verschiedene andere Protagonisten werfen in dieser Ausgabe der Portal Alumni einen Blick auf unterschiedliche Aspekte der zurückliegenden Entwicklung der Universität. Vom Erfolg der Universität zeugt auch die wachsende Zahl der Absolventinnen und Absolventen, die die Universität verlassen. Portal Alumni stellt in der vorliegenden Ausgabe deshalb Absolventen und deren universitäre und berufliche Lebenswege genauer vor und lässt damit zugleich kaleidoskopartig 20 Jahre Studium an der Universität Potsdam Revue passieren.
L-edge spectroscopy of 3d transition metals provides important electronic structure information and has been used in many fields. However, the use of this method for studying dilute aqueous systems, such as metalloenzymes, has not been prevalent because of severe radiation damage and the lack of suitable detection systems. Here we present spectra from a dilute Mn aqueous solution using a high-transmission zone-plate spectrometer at the Linac Coherent Light Source (LCLS). The spectrometer has been optimized for discriminating the Mn L-edge signal from the overwhelming 0 K-edge background that arises from water and protein itself, and the ultrashort LCLS X-ray pulses can outrun X-ray induced damage. We show that the deviations of the partial-fluorescence yield-detected spectra from the true absorption can be well modeled using the state-dependence of the fluorescence yield, and discuss implications for the application of our concept to biological samples.
Irradiating a ferromagnet with a femtosecond laser pulse is known to induce an ultrafast demagnetization within a few hundred femtoseconds. Here we demonstrate that direct laser irradiation is in fact not essential for ultrafast demagnetization, and that electron cascades caused by hot electron currents accomplish it very efficiently. We optically excite a Au/Ni layered structure in which the 30 nm Au capping layer absorbs the incident laser pump pulse and subsequently use the X-ray magnetic circular dichroism technique to probe the femtosecond demagnetization of the adjacent 15 nm Ni layer. A demagnetization effect corresponding to the scenario in which the laser directly excites the Ni film is observed, but with a slight temporal delay. We explain this unexpected observation by means of the demagnetizing effect of a superdiffusive current of non-equilibrium, non-spin-polarized electrons generated in the Au layer.