THE VALENCE FORCE FIELD OF $CX_{3}YZ_{2}$, AND THE VIBRATIONAL SPECTRA OF $CF_{3}NO_{2}$, AND $CBr_{*}NO_{2}$

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1964

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Ohio State University

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Kinetic and potential energy matrix elements are given in analytical form for the vibrations of balanced, non-axially symmetric $CX_{2}NO_{2}$ molecules. The matrix elements may be easily converted for use in $CX_{2}YZ_{2}$ molecules with symmetrically planar $CYZ_{2}. C_{2r}$ symmetry was used and its applicability examined. Potential energy constants obtained for $CF_{3}NO_{2}, CCl_{3}NO_{2}$, and $CBr_{3}NO_{2}$ yield calculated vibrational frequencies which agree with observed values to over 98%. The transferbility and uniquencess of the constants and the significance of the agreement is discussed. Geometry and s-character are examined in terms of the normal coordinate calculation. An empirical relationship is proposed for connecting electronegativity and atomic mass with changes in $YZ_{2}$ deformation frequencies.

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Author Institution: Spectroscopy Group, Propellants Laboratory; Space Sciences Laboratory, University of California; Spectroscopy Group, Picatinny Arsenal

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