On the Existence of FN5, a Theoretical and Experimental Study
Abstract
The possible existence of FN(5) was studied by ab initio electronic structure theory. Calculations were carried out at the MP2/6-31+G(d) and CCSD(T)/aug-cc-pVDZ levels of theory for the N(5)+AsF(6) ion pair and its decomposition to FN(5) and AsF(5). Six different vibrationally stable isomers of FN(5) were identified. Intrinsic reaction coordinate (IRC) and dynamic reaction path (DRP) calculations were used to study the isomerization of FN(5) and its decomposition to FN(3) and N(2). A Rice-Ramsperger-Kassel-Marcus (RRKM) analysis was performed, indicating upper limits to the lifetimes of the FN5 isomers in the nanosecond range. These theoretical predictions were confirmed by an experimental study of the thermolyses of N(5)AsF(6) and N5(2)SnF(6) and the displacement of FN(5) from N(5)SbF(6) with CsF, using FT-IR spectroscopy. In accord with the theoretical predictions, the primary reaction product FN(5) could - not be observed, but its decomposition products FN(3), F(2)N(2), and NF(3) were identified.
Document Details
- Document Type
- Technical Report
- Publication Date
- Feb 11, 2003
- Accession Number
- ADA412561
Entities
People
- Ashwani Vij
- Heather M. Netzloff
- Karl O. Christe
- Mark S. Gordon
- William W. Wilson
Organizations
- Air Force Research Laboratory