BALLHAUSEN INTRODUCTION TO LIGAND FIELD THEORY PDF

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Preface to the title at left, I have tried to give an introduction to that field of chemistry which deals with the spectral and magnetic features of inorganic complexes. It has been my intention not to follow the theory in all its manifestations but merely to describe the basic ideas and applications. This has been done with an eye constantly aimed at the practical and experimental features of the chemistry of the complex ions.

The book is thus primarily intended for the inorganic chemist, but it is true that, in order to follow the exposition, a course in basic quantum mechanics is needed. Simple examples are nearly always used to illustrate the arguments, but the quoted experimental evidence must of necessity be limited.

Nevertheless, in the last chapter an attempt has been made to cover most of the important work so far performed that lies within the scope of the book. However, the field is advancing so rapidly that a complete survey would be outdated before long. Since I am a chemist writing for chemists, my emphasis and notation will probably appear clumsy to the physicists primarily responsible for the theory.

For this I make no excuse. Elegant derivations and condensed notation are in my opinion not desirable in an introduction to a field. Nothing is more dangerous than to force every observation into a fixed framework of ideas. I have tried to present the case for the ligand field theory as it is now understood. It is my personal view that there are really only a few places where we need to revise part of the theory in order to understand the sundry phenomena.

It must always be remembered, however, that the ligand field theory offers only a model of nature, with all the inherent limitations of models. I want particularly to thank, among many others, Dr. Andrew D. Liehr, Mellon Institute, Dr. Harry B. Gray , Columbia University, for numerous discussions and for help with the manuscript. I am also greatly indebted to Mrs. Lise Seifert for her assistance in preparing the manuscript. Finally, I want to thank the editors of Annual Review of Physical Chemistry for permission to draw from the paper written by the late Prof.

Moffitt and myself. Carl J. Ballhausen Contents Preface History of complexes Theories of bonding History of the crystal field approach Orbitals and states Atomic wavefunctions The raising and lowering operators Matrix elements Two-electron operators Term energies General remarks on the method Spin-orbit coupling in a hydrogen-like system..

Spin-orbit coupling in a many-electron case Absolute term intervals Zeeman splitting Selection rules Concept of symmetry operators Nomenclature of symmetry operators Important point groups in inorganic complexes Representations and wave functions The direct product Double groups The Eulerian angles Octahedrai fields Single d electron in a cubic field Weak fields Strong fields Fields of intermediate strength Computation aids Descent in symmetry Equivalence of t2g and p electrons The spectrochemical series Tetragonal fields Trigonal fields Cis, trans and rhombic fields Tetrahedral fields Importance of spin-orbit coupling Spin-orbit coupling,one d electron, octah.

Spin-orbit coupl. Spin-orbit split. The spin Hamiltonian Magnetic susceptibilities General discussion Bonding scheme for an octahedral complex Estimation of wave functions in an MO acheme Band intensities in parity allowed transitions Vibrational spectra Absorption band intens.

Jahn-Teller configurational instabilit Experimental Evidence of the Jahn-Teller Effect.. The Faraday effect Optical rotatory dispersion Stability of complex ions

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Ligand field theory

History Edit Ligand field theory resulted from combining the principles laid out in molecular orbital theory and crystal field theory , which describes the loss of degeneracy of metal d orbitals in transition metal complexes. John Stanley Griffith and Leslie Orgel [5] championed ligand field theory as a more accurate description of such complexes, although the theory originated in the s with the work on magnetism of John Hasbrouck Van Vleck. Griffith and Orgel used the electrostatic principles established in crystal field theory to describe transition metal ions in solution and used molecular orbital theory to explain the differences in metal-ligand interactions, thereby explaining such observations as crystal field stabilization and visible spectra of transition metal complexes. In their paper, they proposed that the chief cause of color differences in transition metal complexes in solution is the incomplete d orbital subshells.

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