Theoretical chemistry fundamental issues

Ilya Prigogine, the founding editor of Advances in Chemical Physics, died May 25, 2003. He was born in Moscow, fled Russia with his family in 1921, and, after brief periods in Lithuania and Germany, settled in Belgium, which was his home for 80 years. His many profound contributions to the theory of irreversible processes included extensions of both macroscopic thermodynamic analysis and statistical mechanical analysis of time-dependent processes and the approach to equilibrium. While sometimes controversial, these contributions were uniformly of outstanding intellectual merit and always addressed to the most fundamental issues they earned him international repute and the Nobel Prize in Chemistry in 1977. Arguably equally important was his creation of a school of theoretical chemical physics centered at the University of Brussels, as well as the mentoring of numerous creative and productive scientists. 

To establish links between the structure of reacting particles and their reactivity is a fundamental issue of theoretical chemistry [30-36], More often the issues on reactivity of atoms and molecules are discussed in connection with elementary reactions. Here, the rate constant and/or reaction cross-section serve as a measure of reactivity. Simultaneously, researchers focus their attention on developing strict principles that enable predicting the influence of the electron structure of reactants on the characteristics of a complex (multistep) chemical transformation... 

The aqueous solvent effects on the rates of Claisen rearrangement have been extensively investigated experimentally and theoretically.2i8-229 Tiie reaction is of particular interest because of its mechanistic and synthetic importance in organic chemistry. In addition, the Claisen rearrangement in chorismate mutase is the only known pericydic reaction catalyzed by a naturally occurring enzyme. 2 A fundamental issue is the dipolar versus the radical nature of the transition state struaure, which will determine the origin of the TS stabilization observed in water. 

At first, the series has a new editor. I, Michael Springborg, am a professor of physical and theoretical chemistry at the University of Saarland in Saarbriicken, Germany, and have research interests on the border between chemistry and physics. The major parts of the research activities of my group concentrate on development and application of theoretical methods and accompanying computer codes for the calculation of properties of materials. Of particular interest to us are structural and electronic properties of systems that are larger than small molecules, but smaller than macroscopic solids. These systems include clusters and colloids, polymers and chain compounds, and surfaces without and with adsorbants. Also fundamental issues like the theoretical treatment of extended systems exposed to electromagnetic fields as well as foundations of density-functional theory are of interest to us. 

Acknowledgments The authors acknowledge the fruitful discussions with Dr. Jan Goetze. This work is a contribution to the Festschrift issue in honor of Prof. Chaer Nascimento, who was co-advisor of the doctoral work of one of the authors (MB). Nascimento s insightful analysis of fundamental issues in quantum chemistry [49] has inspired a whole generation of computational theoretical chemists. 

The study of fire in a compartment primarily involves three elements (a) fluid dynamics, (b) heat transfer and (c) combustion. All can theoretically be resolved in finite difference solutions of the fundamental conservation equations, but issues of turbulence, reaction chemistry and sufficient grid elements preclude perfect solutions. However, flow features of compartment fires allow for approximate portrayals of these three elements through global approaches for prediction. The ability to visualize the dynamics of compartment fires in global terms of discrete, but coupled, phenomena follow from the flow features. 

The theoretical aspects and practical employment of various TLC methodologies have been discussed in detail in excellent books [41,42], biennial reviews published in the Fundamental Reviews issue of the ACS journal Analytical Chemistry [43] and other reviews dealing with special aspects of theory and practical application of TLC [44,45],... 

Like the 1994-issue of the series "Electron Transfer", the second volume again covers various aspects of this fundamental process. The articles are concerned with the experimental and theoretical aspects of electron transfer in chemistry and biology. In the latter, emphasis is given to energy transfer, which is also part of photosynthesis. 

A number of reviews can be consulted for an introduction to the fundamentals both theoretical and practical covering XPS. These include Riggs and Parker (2) and the book by Carlson (3). Electron spectroscopy is reviewed in alternate years in the Fundamental Reviews issue of Analytical Chemistry. The last literature review was published in 1980 (4) and this and previous reviews can be consulted for a coverage of all aspects of the literature of XPS. A number of recent symposia have been held on applications of surface analytical methods in various aspects of materials science such as the symposium on characterization of molecular structures of polymers by photon, electron, and ion probes at the March 1980 American Chemical Society meetings in Houston ( 5) and the International Symposium on Physiochemical Aspects of Polymer Surfaces at this meeting as well as the symposium on industrial applications of surface analysis of which this article is a part. Review articles on various applications of XPS in materials science are listed in Table I. 

Every discipline has particular problems with some philosophical coloring. Those in quantum theory are famous those in psychology seem endless those in biology and economics seem more sparse and esoteric. If, for whatever reason, one s concern is the conceptual or theoretical problems of a particular science, there is no substitute for that science, and chemistry is just one among others. Certain sciences naturally touch on substantive areas of traditional philosophical concern quantum theory on metaphysics, for example, psychology on the philosophy of mind, and economics and statistics on theories of rationality. In these cases, there is a special interest in particular sciences because they may reform prior philosophical theories or recast philosophical issues or, conversely, because philosophy may inform these subjects in fundamental ways. That is not true, in any obvious way, of chemistry. 

The first coordination compound synthesized in the laboratory was Berlin blue, prepared in 1704 by Disbach, so it is obvious that preparative coordination chemistry has an extensive history. At times syntheses were unpredictable, unsuccessful, or unreported. Today, coordination chemists plan their syntheses by applying fundamental chemical principles and theories. For this reason we begin with a chapter describing classical theoretical concepts that are important in the synthesis of coordination compounds before we consider other issues such as solvents, reactive intermediates, reagents, etc. 

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