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Article Dans Une Revue Journal of Chemical Physics Année : 2013

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

J. G. Hill
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K. A. Peterson
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Résumé

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.

Dates et versions

hal-00808497 , version 1 (05-04-2013)

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Citer

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