Lecture20 - Atomic configurations Means of describing the...

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1 Physical Chemistry Lecture 20 Russell-Saunders Terms, Hund’s Rules, Spin-orbit Coupling, Spectroscopy Atomic configurations Means of describing the energy situation of a multi-electron system Independent-electron energy is a sum of hydrogenic energies of the electrons Add first-order correction for electron-electron repulsion Combinations of Coulomb repulsion integrals and exchange integrals Wave functions of indistinguishable electrons are antisymmetric combinations of products of one-electron wave functions Slater-type orbitals Configurations may be parsed into terms Terms from the same configuration differ in energy because of the contributions of Coulomb and exchange integrals To specify possible states, must determine All terms arising from a particular configuration Relative energies of terms Determining Russell-Saunders terms Angular momentum found by adding angular momenta of subsystems Add orbital and spin angular momentum independently to give total orbital angular momentum and total spin Use Unsöld’s theorem to simplify determination
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This note was uploaded on 02/02/2012 for the course CHEM 444 taught by Professor Dybowski,c during the Fall '08 term at University of Delaware.

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Lecture20 - Atomic configurations Means of describing the...

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