01s_transmxel

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Unformatted text preview: MIT OpenCourseWare http://ocw.mit.edu 5.80 Small-Molecule Spectroscopy and Dynamics Fall 2008 For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms . Lecture #1 Supplement Contents A. Spectroscopic Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1. H. N. Russell, A. G. Shenstone, and L. A. Turner, “Report on Notation for Atomic Spectra,” 1 2. W. F. Meggers and C. E. Moore, “Report of Subcommittee f (Notation for the Spectra of Diatomic Molecules)” . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 3. F. A. Jenkins, “Report of Subcommittee f (Notation for the Spectra of Diatomic Molecules)” 2 4. No author, “Report on Notation for the Spectra of Polyatomic Molecules” . . . . . . . . . . 2 B. Good Quantum Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 C. Perturbation Theory and Secular Equations . . . . . . . . . . . . . . . . . . . . . . . . . 3 D. Non-Orthonormal Basis Sets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 E. Transformation of Matrix Elements of any Operator into Perturbed Basis Set . . . . 7 A. Spectroscopic Notation The language of spectroscopy is very explicit and elegant, capable of describing a wide range of unanticipated situations concisely and unambiguously. The coherence of this language is diligently preserved by a succession of august committees, whose agreements about notation are codified. These agreements are often published as authorless articles in major journals. The following list of citations include the best of these notation-codifying articles. 1. H. N. Russell, A. G. Shenstone, and L. A. Turner, “Report on Notation for Atomic Spectra,” Phys. Rev. 33 , 900-906 (1929). At an informal meeting of spectroscopists at Washington in April, 1928, the writers of this report were requested to draw up a scheme for the clarification of spectroscopic notation. After much discussion and correspondence with spectroscopists both in this country and abroad we are able to present the following recommendations. The analysis of a spectrum can be of three different types. (1) A multiplet, or in many cases a level, analysis. This includes the determination of the types of terms ( S , P , D , etc.), the multiplicities, and the inner quantum numbers of the individual levels when possible. (2) A configuration analysis. The description of the electron configuration with which the spectroscopic terms are to be correlated as given by Hund in this book. (3) A series analysis. The identification of series of terms and finding of their limits. A complete notation must be capable of adequately expressing the results of all three types of analysis whether complete or only partial....
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This note was uploaded on 11/28/2011 for the course CHEM 5.74 taught by Professor Robertfield during the Spring '04 term at MIT.

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01s_transmxel - MIT OpenCourseWare http://ocw.mit.edu 5.80...

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