NEW PERSPECTIVE ON PF$_n$ ($n$=1--5) FROM THE RECOUPLED PAIR BONDING MODEL: A QUANTUM CHEMICAL STUDY
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Date
2010
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Ohio State University
Abstract
Structures of the PF$_n$ family ($n$=1--5) were characterized with high level RCCSD(T) coupled cluster theory calculations using triple and quadruple zeta quality correlation consistent basis sets. In addition to accounting for the well-known ground states of PF through PF$_5$, insight from the recoupled pair bonding model also led to locating a previously unknown $^3B_1$ state of PF$_3$, which lies about 90 kcal/mol above PF$_3$($^1A_1$) but is still bound with respect to PF$_2$($^2B_1$)+F($^2P$) by about 40 kcal/mol. We also revisited the less-studied $C_{3v}$ local minimum on the PF$_4$ doublet surface and characterized the transition state for interconversion to the $C_{2v}$ global minimum. The energetics suggest that both PF$_3$($^3B_1$) and $C_{3v}$ PF$_4$($^2A_1$) are potentially observable in the laboratory. The trends in the bond dissociation energies and relative energy differences of the PF$_n$ family are very consistent with predictions from the recoupled pair bonding model.
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Author Institution: Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801