Quantum-chemical insights into mixed-valence systems: within and beyond the Robin-Day scheme

In mixed-valence (MV) systems essentially identical, more or less electronically coupled, redox centres are brought into formally different oxidation states by removal or addition of an electron. Depending on the strength of electronic coupling, an electron or a hole is either concentrated on one of the redox centres, or it is symmetrically delocalised onto several sites, or the situation is somewhere in between, which leads to the classification system for MV systems introduced by Melvin Robin and Peter Day. These different characteristics are of fundamental importance for the understanding of electron transfer processes. Applications of quantum-chemical methods to aid the classification and to unravel the nature of the electronic structure and spectroscopic data of both organic and transition-metal MV systems, have gained tremendous importance over the last two decades. In this review, we emphasise the prerequisites the quantum-chemical methods need to fulfill to successfully describe MV systems close to the borderline between Robin–Day classes II and III. These are, in particular, a balanced treatment of exchange, dynamical and non-dynamical correlation effects, as well as consideration of the crucial influence of the (solvent or solid-state) environment on the partial localisation of charge. A large variety of applications of quantum-chemical methods to both organic and inorganic MV systems are critically appraised here in view of these prerequisites. Practical protocols based on a combination of suitable density functional methods with continuum or non-continuum solvent models provided good agreement with experimental data for the ground states and the electronic excitations of a large range of MV systems close to the borderline. Recent applications of such methods have highlighted the crucial importance of conformational effects on electronic coupling, all the way to systems where conformational motion may cause a thermal mixing of class II and class III situations in one system.DFG, EXC 314, Unifying Concepts in CatalysisDFG, GRK 1221, Steuerung elektronischer Eigenschaften von Aggregaten pi-konjugierter Molekül

Green Open Access in Mathematik und Astronomie

Taubert NC. Green Open Access in Mathematik und Astronomie. In: Parthey H, Umstätter W, eds. Forschung und Publikation in der Wissenschaft. Jahrbuch Wissenschaftsforschung. Vol 2013. Berlin: Wissenschaftlicher Verlag Berlin (wVB); 2014: 42-75

Structured identification of business improvement opportunities using Life Cycle Assessment : A case study in the gas turbine industry

Part of: Seliger, Günther (Ed.): Innovative solutions : proceedings / 11th Global Conference on Sustainable Manufacturing, Berlin, Germany, 23rd - 25th September, 2013. - Berlin: Universitätsverlag der TU Berlin, 2013. - ISBN 978-3-7983-2609-5 (online). - http://nbn-resolving.de/urn:nbn:de:kobv:83-opus4-40276. - pp. 205–209.In the last two decades the power sector has been adopting environmental conscious practices in several business areas and processes. Bridging the identification of environmental “hot-spots” in the product life cycle and the implementation and execution of an environmental management system requires an integrated approach starting with a Life Cycle Assessment to identify the improvement potentials; then analyzing the current management and product development systematics in use, and finally mapping the environmental practices against the improvement potential. The improvement tracking will be embedded in the management system as an Environmental Improvement Roadmap, mapping the efforts required to realize the goals. The methodology has been implemented in pilot studies, focusing on the processes performed in-house to enable further decisions on process alternatives and providing reliable information for strategic decisions within the Siemens Environmental Product Portfolio

Computational and spectroscopic studies of organic mixed-valence compounds: where is the charge?

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.This article discusses recent progress by a combination of spectroscopy and quantum-chemical calculations in classifying and characterizing organic mixed-valence systems in terms of their localized vs.delocalized character. A recently developed quantum-chemical protocol based on non-standard hybrid functionals and continuum solvent models is evaluated for an extended set of mixed-valence bis-triarylamine radical cations, augmented by unsymmetrical neutral triarylamine-perchlorotriphenylmethyl radicals. It turns out that the protocol is able to provide a successful assignment to class II or class III Robin-Day behavior and gives quite accurate ground- and excited-state properties for the radical cations. The limits of the protocol are probed by the anthracene-bridged system8, where it is suspected that specific solute–solvent interactions are important and not covered by the continuum solvent model. Intervalence charge-transfer excitation energies for the neutral unsymmetrical radicals are systematically overestimated, but dipole moments and a number of other properties are obtained accurately by the protocol.DFG, GRK 1221, Steuerung elektronischer Eigenschaften von Aggregaten pi-konjugierter Molekül