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- Title
Reaction mechanism of platinum dimer cation with ammonia based on the relativistic density functional study.
- Authors
Xu, Dan; Chen, Xian‐Yang; Wang, Shu‐Guang
- Abstract
The gas-phase reactions between Pt<STACK>2+</STACK> and NH3 have been investigated using the relativistic density functional approach (ZORA-PW91/TZ2P). The quartet and doublet potential energy surfaces of Pt<STACK>2+</STACK> + NH3 have been explored. The minimum energy reaction path proceeds through the following steps: Pt<STACK>2+</STACK>(4Σu) + NH3 → q-1 → d-2 → d-3 → d-4 → d-Pt2NH+ + H2. In the whole reaction pathway, the step of d-2 → d-3 is the rate-determining step with a energy barrier of 36.1 kcal/mol, and exoergicity of the whole reaction is 12.0 kcal/mol. When Pt2NH+ reacts with NH3 again, there are two rival reaction paths in the doublet state. One is degradation of NH<STACK>4+</STACK> and another is loss of H2. In the case of degradation of NH<STACK>4+</STACK>, the activation energy is only 3.4 kcal/mol, and the overall reaction is exothermic by 8.9 kcal/mol. Thus, this reaction is favored both thermodynamically and kinetically. However, in the case of loss of H2, the rate-determining step's energy barrier is 64.3 kcal/mol and the overall reaction is endothermic by 8.5 kcal/mol, so it is difficult to take place. Predicted relative energies and barriers along the suggested reaction paths are in reasonable agreement with experimental observations. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007
- Subjects
PLATINUM; DIMERS; OLIGOMERS; AMMONIA; CATIONS; DENSITY
- Publication
International Journal of Quantum Chemistry, 2007, Vol 107, Issue 10, p1985
- ISSN
0020-7608
- Publication type
Article
- DOI
10.1002/qua.21346