$\nu_{1}+\nu_{5}$ OF HCCN: DETERMINATION OF THE $\nu_{5}$ VIBRATIONAL ENERGY

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1999

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Ohio State University

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The high resolution infrared spectrum of HCCN in the region $3338-3382cm^{-1}$ has been observed by infrared kinetic spectroscopy. The spectrum is assigned as the combination band $\nu_{1}+\nu_{5}$ of the quasilinear molecule HCCN with the origin at $3355.510(9)cm^{-1}$. Based on information from the $\nu_{1}+\nu_{5}-\nu_{5}$ $spectrum^{[1]}$, the energy of the lowest excited state with angular momentum about the a-axis, $\nu_{5}$, is determined to be $128.913(9)cm^{-1}$. This value is lower than the results obtained by means of relative intensity measurements on the millimeter-wave $spectra^{[2]}$ $[145(15)cm^{-1}]$ or from similar relative intensity measurements on the IR $spectra^{[1]}$ $[187(20)cm^{-1}]$. The present values of the energy for $\nu_{5}$ predicts a barrier to linearity similar to that obtained from the corresponding band of $DCCN^{[3]}$ and is higher than that found by McCarthy $et al.^{[2]}$. $^{[1]}$ C.L. Morter, S.K. Farhat and R.F. Cul, Chem. Phys. Lett. 207, 153(1993);$^{[2]}$ M.C. McCarthy, C.A.Gottlieb, A.L. Cooksy and P. Thadius, J. Chem. Phys. 103(18), 7779(1995);$^{[3]}$ Fuge Sun, A. Kosterev, G. Scott, V. Litosh, and R. F. Curl, J. Chem. Phys. 109(20), 8851(1998).

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Author Institution: Chemistry Department and Rice Quantum Institute, Rice University

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