The molecular structure of AgBr2 and AgBr2+. A benchmark CASSCF, CASPT2, and averaged coupled pair functional study
Article first published online: 15 MAY 2012
Copyright © 2012 Wiley Periodicals, Inc.
International Journal of Quantum Chemistry
Special Issue: Mexican Theoretical Physical Chemistry Meetings
Volume 112, Issue 22, pages 3559–3563, 15 November 2012
How to Cite
Ramírez-Solís, A. (2012), The molecular structure of AgBr2 and AgBr2+. A benchmark CASSCF, CASPT2, and averaged coupled pair functional study. Int. J. Quantum Chem., 112: 3559–3563. doi: 10.1002/qua.24167
- Issue published online: 16 OCT 2012
- Article first published online: 15 MAY 2012
- Manuscript Accepted: 18 APR 2012
- Manuscript Revised: 16 APR 2012
- Manuscript Received: 13 MAR 2012
The ground states of AgBr2 and AgBr2+ have been predicted to be 2B2 and 1A1 bent structures (θ = 67° and θ = 47°, respectively) using complete active space self-consistent field (CASSCF) and multireference second order perturbation theory (J. Chem. Phys., 1999, 111, 8925). Because CuF2, CuCl2, and AgCl2 are known to be linear, the ground states of AgBr2 and AgBr2+ have been studied through benchmark ab initio CASSCF(21,15), multireference second-order perturbation theory and averaged coupled pair functional calculations using very large and especially developed valence basis sets. The bent nature of the ground state of the AgBr2+ ion is confirmed, but for AgBr2 the absolute minimum of the ground state is found to be 2Πg in the linear centrosymmetric structure with the present large optimized basis sets at all levels of theory. Also, a significant Ag-Br bond length reduction was obtained for the cation with respect to the previous value. These results show the crucial role played by the quality of the valence atomic basis sets for this type of transition metal molecules on key properties such as the equilibrium geometry. New equilibrium geometries, vibrational frequencies and ionization potentials are presented. © 2012 Wiley Periodicals, Inc.