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ROTATIONAL CONSTANTS OF MOLECULES WITH DOUBLE-MINIMUM POTENTIALS.

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/15719

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Title: ROTATIONAL CONSTANTS OF MOLECULES WITH DOUBLE-MINIMUM POTENTIALS.
Creators: Watson, J. K. G.
Issue Date: 1969
Abstract: The rotational constants of molecules in successive levels of a symmetric double-minimum potential show a characteristic staggering that is fairly well represented by a term in $<Q^{2}>$, where Q is the coordinate for the double-minimum motion. A precise representation can be obtained by adding a term in $<Q^{4}>$, but the observed coefficients of $<Q^{4}>$ are much larger than expected from the expansions of the moments of inertia.$^{1}$ The present work uses a term in $<P^{2}>$ rather than in $<Q^{4}>, P$ being the momentum conjugate to Q. This term in $<P^{2}>$ originates from the second-order effects of Coriolis interaction with the other vibrations. For a quartic potential with a negative quadratic barrier the two alternative expressions provide identical fits to the observed constants, because the virial theorem gives a linear relation between $<Q^{2}>, <Q^{4}>$ and $<P^{2}>$. Preliminary calculations show that the observed coefficients of $<P^{2}>$ are of the correct order of magnitude for this Coriolis mechanism.
URI: http://hdl.handle.net/1811/15719
Other Identifiers: 1969-H-3
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