HSIN: CALCULATED SPECTROSCOPIC PROPERTIES AND BARRIER HEIGHT TO ISOMERIZATION FOR HSIN

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1994

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Ohio State University

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Quite recently, the matrix-isolation IR spectrum of HSiN was reported by Maier and $Glatthaar.^{1}$ They observed the stretching vibrations of $H^{28}$SiN and $D^{28}SiN$ (in parenthesis) at 2152.2 (1580.5) and $1162.2 (1145.4) cm^{-1}$. We have carried out CCSD(T)$^{2}$ and internally contracted $MRCI^{3}$ calculations. The former yielded $\nu_{1} = 2117 (1563), \nu_{2}$ = 157 (117) and $\nu_{3} = 1129(1117) cm^{-1}$. The barrier height (BH) for isomerization to the more stable HNSi species was obtained to be $4107 cm^{-1}$ (MRCI), CCSD(T) calculations yield a slightly lower value of $3927 cm^{-1}$ while $MP2^{4}$ performs poorly (BH: $14015 cm^{-1}$).

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$^{1}$G. Maier and J. Glatthaar. Angew. Chem. 106, 486 (1994). $^{2}$Coupled Cluster method with single and double excitation operators and a quasiperturbative treatment of the effects of connected triple excitations; K. Raghavachari, G.W. Trucks, J.A. Pople and M. Head-Gadon, Chem. Phys. Lett. 157, 479 (1959) $^{3}$MRCI. Multiconfiguration reference configuration interaction; H.J. Werner and P.J. Knowles, J. Chem. Phys. 89, 5803 (1988). $^{4}$Second-order perturbation theory according to Meller and Plesset.
Author Institution: Institut f\""{u}r Physikalische Chemie, der Universit\""{a}t

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