Cluster chemistry dynamics

Houk RJT, Jacobs BW, El Gabaly F, Chang NN, Talec AA, Graham DD, House SD, Robertson IM, Allendorf MD. Silver cluster formation, dynamics, and chemistry in metal-organic frameworks, Nano Lett. 2009, 9(10), 3413-3418. 

P. Braunstein, L. A. Oro and P. R. Raithby (eds.), Metal Clusters in Chemistry, vol. 1 Molecular Metal Cluster, vol. 2 Catalysis and Dynamics and Physical Properties of Metal Clusters, vol. 3 Nanomaterials and Solid-state Cluster Chemistry, Wiley-VCH, Weinheim, 1999. 

Caveats. Those familiar with cluster chemistry will mark the absence of cluster synthesis, framework dynamics and reactivity. Considerable information exists and these topics for selected cluster types are well developed in cluster reviews and edited volumes. However, our focus on electronic structure is deliberate. We wished to compare and contrast geometric and electronic structure across the large sweep of element composition and cluster size up to and including bulk materials. To keep the book of manageable size relative to a typical one-semester advanced course yet... 

Robert Benny Gerber obtained his B.Sc. in chemistry from the Hebrew University of Jerusalem in 1965. He did his doctoral research with C.A. Coulson at Oxford University in 1968, and was a Postdoctoral Research Fellow with Martin Karplus at Harvard University. Since 1976 he has been on the faculty of the Hebrew University of Jerusalem, where he holds the Saerre K. and Louis P. Fiedler Chair in Chemistry. Since 1990 he is also Professor of Chemistry at the University of California at Irvine. Gerber s current research interests include vibrational spectroscopy calculations for large molecules new molecules of the noble gas elements and their formation dynamics photochemical reactions in low-temperature matrices and clusters and dynamics of atmospherically important processes. 

The characterization of structure and dynamics in metal carbonyl cluster chemistry has understandably been based around single-crystal X-ray diffraction and NMR spectroscopic studies, respectively. As has been shown in the earlier part of this chapter, these sources of data can be used in conjunction to provide a coherent picture of the possible molecular configurations of a given species and the processes by which they interconvert, at least in favorable cases. In general however, it is not possible to determine the geometric structures of these species in solution, nor to obtain direct experimental evidence to confirm that the same structure(s) obtain in solution as in the solid state. Fortunately the rebirth and exploitation of X-ray absorption spectroscopy (XAS) and in particular the application of synchrotron X-ray sources and improved methods of data analysis to EXAFS (Extended X-ray Absorption Eine Structure) spectroscopy has provided exactly this sort of experimental evidence. In this section we provide selective coverage of such work as relates to the structure and dynamics of metal carbonyl clusters. 

The first volume of this book covers the topics of molecular metal clusters, the second volume contains sections on metal clusters in catalysis and dynamic and physical properties of metal clusters. Volume 3 covers the chemistry of nanomaterials and of solid-state clusters. It also contains an update of the reviews published on metal clusters in the last ten years, and finally presents a view on further developments in cluster chemistry leading into the next millennium. In general, the sections within the book contain a blend of experimental results together with an analysis of theoretical aspects of the work. In some instances, closely related areas have been discussed by several authors and here a complementary diversity of views is offered. The editors wish to thank the authors for their contributions to this book and the numerous scientists who have been involved in Network activities, they have all greatly assisted in the project by their vitality and enthusiasm for this developing area. 

Gerber R B, McCoy A B and Garcia-Vela A 1995 Dynamics of photoinduced reactions in the van der Waals and in the hydrogen-bonded clusters Femtosecond Chemistry Proc. Berlin Conf. Femtosecond Chemistry (Berlin, March 1993) ed J Manz and L Woeste (Weinheim Verlag Chemie) pp 499-531... 

In this brief review we illustrated on selected examples how combinatorial computational chemistry based on first principles quantum theory has made tremendous impact on the development of a variety of new materials including catalysts, semiconductors, ceramics, polymers, functional materials, etc. Since the advent of modem computing resources, first principles calculations were employed to clarify the properties of homogeneous catalysts, bulk solids and surfaces, molecular, cluster or periodic models of active sites. Via dynamic mutual interplay between theory and advanced applications both areas profit and develop towards industrial innovations. Thus combinatorial chemistry and modem technology are inevitably intercoimected in the new era opened by entering 21 century and new millennium. 

Pohorille, A. Wilson, M.A. Isomerization reactions at aqueous interfaces, in Reaction Dynamics in Clusters and Condensed Phases — The Jerusalem Symposia on Quantum Chemistry and Biochemistry, lortner, J. Levine, R. Pullman, B., Eds., vol. 26. Kluwer Dordrecht, 1993, p. 207... 

In this article we have summarized the use of both photochemical and more classical thermal kinetics techniques to deduce the nature of intermediates in the ambient temperature, fluid solution chemistry of several triruthenium clusters. In some cases the photochemically generated intermediates appear to be the same as those proposed to be formed along thermal reaction coordinates, while in other cases unique pathways are the results of electronic excitation. The use of pulse photolysis methodology allows direct observation, and the measurement of the reaction dynamics of such transients and provides quantitative evaluation of the absolute reactivities of these species. In some cases, detailed complementary information regarding... 

Abstract Amino acids are the basic building blocks in the chemistry of life. This chapter describes the controllable assembly, structures and properties of lathanide(III)-transition metal-amino acid clusters developed recently by our group. The effects on the assembly of several factors of influence, such as presence of a secondary ligand, lanthanides, crystallization conditions, the ratio of metal ions to amino acids, and transition metal ions have been expounded. The dynamic balance of metalloligands and the substitution of weak coordination bonds account for the occurrence of diverse structures in this series of compounds. 

First-principles (or ah initid) molecular dynamics, the direct combination of DFT with classical molecular dynamics (MD), was introduced in 1985 in a seminal paper by Car and Parrinello [9]. This novel scheme has first been applied to the study of metal clusters [20] and amorphous and liquid silicon [21] but has since moved rapidly into chemistry [22] and biology [23, 24], CP-MD of-... 

The basic theories of physics - classical mechanics and electromagnetism, relativity theory, quantum mechanics, statistical mechanics, quantum electrodynamics - support the theoretical apparatus which is used in molecular sciences. Quantum mechanics plays a particular role in theoretical chemistry, providing the basis for the valence theories which allow to interpret the structure of molecules and for the spectroscopic models employed in the determination of structural information from spectral patterns. Indeed, Quantum Chemistry often appears synonymous with Theoretical Chemistry it will, therefore, constitute a major part of this book series. However, the scope of the series will also include other areas of theoretical chemistry, such as mathematical chemistry (which involves the use of algebra and topology in the analysis of molecular structures and reactions) molecular mechanics, molecular dynamics and chemical thermodynamics, which play an important role in rationalizing the geometric and electronic structures of molecular assemblies and polymers, clusters and crystals surface, interface, solvent and solid-state effects excited-state dynamics, reactive collisions, and chemical reactions. 

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