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 |
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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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