Quantum-chemical study of the effect of ligands on the structure and properties of gold clusters
- Authors: Golosnaya M.N.1, Pichugina D.A.1, Oleinichenko A.V.1, Kuz’menko N.E.1
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Affiliations:
- Department of Chemistry
- Issue: Vol 91, No 2 (2017)
- Pages: 346-350
- Section: Structure of Matter and Quantum Chemistry
- URL: https://journals.rcsi.science/0036-0244/article/view/169278
- DOI: https://doi.org/10.1134/S0036024417020108
- ID: 169278
Cite item
Abstract
The structures of [Au4(dpmp)2X2]2+clusters, where Х =–C≡CH,–СН3,–SCH3,–F,–Cl,–Br,–I, dpmp is bis((diphenylphosphino)methyl)(phenyl)phosphine, are calculated at the level of density functional theory with the PBE functional and a modified Dirac–Coulomb–Breit Hamiltonian in an all-electron basis set (Λ). Using the example of [Au4(dpmp)2(С≡CС6Н5)2]2+, the interatomic distances and bond angles calculated by means of PBE0/LANL2DZ, TPSS/LANL2DZ, TPSSh/LANL2DZ, and PBE/Λ are compared to X-ray crystallography data. It is shown that PBE/Λ yields the most accurate calculation of the geometrical parameters of this cluster. The ligand effect on the electronic stability of a cluster and the stability in reactions of decomposition into different fragments is studied, along with the capability of ligand exchange. Stability is predicted for [Au4(dpmp)2F2]2+ and [Au4(dpmp)2(SCH3)2]2+, while [Au4(dpmp)2I2]2+ cluster is unstable and its decomposes into two identical fragments is supposed.
Keywords
About the authors
M. N. Golosnaya
Department of Chemistry
Email: daria@phys.chem.msu.ru
Russian Federation, Moscow, 119991
D. A. Pichugina
Department of Chemistry
Author for correspondence.
Email: daria@phys.chem.msu.ru
Russian Federation, Moscow, 119991
A. V. Oleinichenko
Department of Chemistry
Email: daria@phys.chem.msu.ru
Russian Federation, Moscow, 119991
N. E. Kuz’menko
Department of Chemistry
Email: daria@phys.chem.msu.ru
Russian Federation, Moscow, 119991