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

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

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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.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Hill, Dr John
Authors: Hill, J.G., Mitrushchenkov, A.O., and Peterson, K.A.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of Chemical Physics
Publisher:American Institute of Physics
ISSN:0021-9606
ISSN (Online):1089-7690
Published Online:05 April 2013
Copyright Holders:Copyright © 2013 American Institute of Physics
First Published:First published in Journal of Chemical Physics 138(13):134314
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher

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