THE ANALYSIS OF ROVIBRATION SPECTRA BY MEANS OF COMPUTER CALCULATED BAND CONTOURS.

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1968

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Ohio State University

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Given proposed values of inertial, centrifugal distortion, and spin interaction constants, the programme calculates eigenvalues, eigenvectors, and differentials with respect to the constants, for both states. Allowed transitions, of appreciable intensity, consistent with the declared band type, are detected and associated frequencies collated with any assigned observed transition frequencies made available as input. The differentials and observed and calculated transition frequencies are then available for least squares analysis to generate those constants, and band origin, which achieve improved agreement between theoretical and experimental transition frequencies or combination differences automatically abstracted from the available data. Both modes permit independent variation of selected constants of either state. In addition the transition frequencies can be used in conjunction with variation of selected constants of both states and the band origin. There are facilities for obtaining tables at any stage in these procedures. The tables include calculated frequencies whether or not an observed counterpart exists, with the assignment and calculated intensity of each line, of use in assisting assignment of further observed transitions. One can also require the production of band envelopes under control of line shape and slit scan characteristics supplied as input.

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Author Institution: Department of Chemistry, The University

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