Chemistry from First Principles

ISBN-13: 9789048179077 / Angielski / Miękka / 2010 / 321 str.

Jan C. a. Boeyens

Opis

The book consists of two parts: A summary and critical examination of chemical theory as it developed from early beginnings through the dramatic events of the twentieth century, and a reconstruction based on a re-interpretation of the three seminal theories of periodicity, relativity and quantum mechanics in chemical context. Anticipating the final conclusion that matter and energy are special configurations of space-time, the investigation starts with the topic of relativity, the only theory that has a direct bearing on the topology of space-time and which demonstrates the equivalence of energy and matter and a reciprocal relationship between matter and the curvature of space. Re-examination of the first quantitative model of the atom, proposed by Bohr, reveals that this theory was abandoned before it had received the attention it deserved. It provided a natural explanation of the Balmer formula that firmly established number as a fundamental parameter in science, rationalized the interaction between radiation and matter, defined the unit of electronic magnetism and produced the fine-structure constant. These are not accidental achievements and in reworking the model it is shown, after all, to be compatible with the theory of angular momentum, on the basis of which it was first rejected with unbecoming haste. The Sommerfeld extension of the Bohr model was based on more general quantization rules and, although more successful at the time, is demonstrated to have introduced the red herring of tetrahedrally directed elliptic orbits, which still haunts most models of chemical bonding. The gestation period between Bohr and the formulation of quantum mechanics was dominated by the discovery and recognition of wave phenomena in theories of matter, to the extent that all formulations of the quantum theory developed from the same classical-mechanical background and the Hamiltonian description of multiply-periodic systems. The reasons for the fierce debates on the interpretation of phenomena such as quantum jumps and wave models of the atom are discussed in the context of later developments. The successful, but unreasonable, suppression of the Schrodinger, Madelung and Bohm interpretations of quantum theory is shown not to have served chemistry well. The inflated claims about uniqueness of quantum systems created a mystique that continues to frighten students of chemistry. Unreasonable models of electrons, atoms and molecules have alienated chemists from their roots, paying lip service to borrowed concepts such as measurement problems, quantum uncertainty, lack of reality, quantum logic, probability density and other ghostlike phenomena without any relevance in chemistry. In fact, classical and non-classical systems are closely linked through concepts such as wave motion, quantum potential and dynamic variables. The second part of the book re-examines the traditional concepts of chemistry against the background of physical theories adapted for chemistry. An alternative theory is formulated from the recognition that the processes of chemistry happen in crowded environments that promote activated states of matter. Compressive activation, modelled by the methods of Hartree-Fock-Slater atomic structure simulation, leads to an understanding of elemental periodicity, the electronegativity function and covalence as a manifestation of space-time structure and the golden ratio. Molecular structure and shape are related to orbital angular momentum and chemical change is shown to be dictated by the quantum potential. The empirical parameters used in computer simulations such as molecular mechanics and dynamics are shown to derive in a fundamental way from the relationship between covalence and the golden ratio, which also explains the physical basis of Pauli s exclusion principle for the first time."

Recenzje

From the reviews:

"This book is deeply thought-provoking and sets itself the task of taking a critical look at the arcane world of quantum mechanics especially in its applications to the realm of chemistry. ... This groundbreaking book which is not heavily mathematical is certainly not be missed by anyone with an interest in quantum theory." (Dennis Rouvray, Chemistry World, March, 2009)

Spis treści

Part I: A New Look at Old Theories

1. Historical Perspective

2. The Important Concepts
     2.1 The Principle of Relativity
     2.2 The Old Quantum Theory
     2.3 Wave-Particle Duality
     2.4 Orbital Angular Momentum
     2.5 The Quantum Theory
     2.6 Atomic Shape
     2.7 Chemical Bonding

3. The Quantum Quandary
     3.1 The Classical Background
     3.2 The Copenhagen Orthodoxy
     3.3 The Schrödinger Interpretation
     3.4 The Hydrodynamic Alternative
     3.5 Bohmian Mechanics
     3.6 Atomic Theory

Part II: Alternative Theory

4. The Periodic Laws
     4.1 Nuclides and Nuclear Structure
     4.2 Chemical Elements and Atomic Structure
     4.3 The Golden Ratio

5. Chemical Interaction
     5.1 The Valence State
     5.2 Electronegativity
     5.3 Chemical Cohesion

6. Molecular Structure
     6.1 Molecular Shape
     6.2 Stereoisomerism
     6.3 Molecular Modelling

7. Chemical Change
     7.1 The Holistic Molecule
     7.2 Molecular Rearrangement
     7.3 Reaction Mechanisms

8. Future Outlook

Blurb

Chemistry from First Principles is written for any chemist who requires a fundamental understanding of the complexities of chemistry. It provides a clear interpretation of chemical theory from first principles.

This book examines the appearance of matter in its most primitive form, from the vacuum and the diversity that results from the fusion of elementary units in the genesis of atomic matter; considers the empirical rules of chemical affinity that regulate the synthesis and properties of molecular matter; analyzes the compatibility of the theories of chemistry with the quantum and relativity theories of physics; formulates a consistent theory, based on clear physical pictures and manageable mathematics, to account for chemical concepts such as the structure and stability of atoms and molecules, the periodicity of nuclides and elements, valence states, activation and chemical reactivity, electronegativity and general covalency, the exclusion principle, electronic energy, orbital angular momentum and spin in relation to molecular shape, torsional rigidity, chirality and molecular modeling; explains the self-similarity between space-time, nuclear structure, covalent assembly, biological growth, planetary systems and galactic conformation.

Chemistry from First Principles is an essential guide for students of chemistry who lack the knowledge in higher mathematics considered necessary to grasp the basic principles of chemical theory, teachers of chemistry who are forced to preach concepts which they poorly understand, and any scientist who is seeking a true understanding of chemistry through logical concepts.