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Ab initio ro-vibrational spectroscopy of the group 11 cyanides: CuCN, AgCN, and AuCN

Abstract : Accurate near-equilibrium potential energy and dipole moment functions have been calculated for the linear coinage-metal cyanides CuCN, AgCN, and AuCN using coupled cluster methods and sequences of correlation consistent basis sets. The explicitly correlated CCSD(T)-F12b method is used for the potential energy surfaces (PESs) with inclusion of core correlation, and is combined with contributions from molecular spin-orbit coupling, scalar relativity, and effects due to higher order electron correlation. The resulting composite PESs are used in both perturbative and variational calculations of the ro-vibrational spectra. In addition to accurate equilibrium geometries, the ro-vibrational spectra are predicted, which are found to be relatively intense in the 200-600 cm−1 range due to the bending and metal-carbon stretching modes. The CN stretch near 2165 cm−1 is also predicted to carry enough intensity to allow its observation by experiment. A strong Fermi-resonance is predicted between the first overtone of the bend and the fundamental of the metal-carbon stretch for both CuCN and AgCN. The heats of formation at 0 K are predicted from their calculated atomization energies to be 89.8, 88.6, and 104.5 kcal mol−1 for CuCN, AgCN, and AuCN, respectively.
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Contributor : Alexander Mitrushchenkov <>
Submitted on : Friday, April 5, 2013 - 3:24:03 PM
Last modification on : Friday, June 19, 2020 - 7:52:04 PM

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J. G. Hill, Alexander Mitrushchenkov, K. Peterson. Ab initio ro-vibrational spectroscopy of the group 11 cyanides: CuCN, AgCN, and AuCN. Journal of Chemical Physics, American Institute of Physics, 2013, 138 (13), pp.134314. ⟨10.1063/1.4798638⟩. ⟨hal-00808497⟩



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