Experimental and ab Initio Study of the Infrared Spectra of Ionic Species Derived from PF5, PF3 and F3PO and Trapped in Solid Neon

Published

June 1, 1998

Author(s)

C Lugez, Marilyn E. Jacox, R A. King, H F. Schaefer

Abstract

When a Ne:PF₅ or a Ne:PF₃ is codeposited a 5 K with a beam of neon atoms that have been excited in a microwave discharge, the infrared spectrum of the resulting solid shows a complicated pattern of new absorptions. Little fragmentation of PF₅ into PF₃ occurs, but several of the absorptions can be tentatively attributed to PF₄. The results of extensive ab initio calculations of the vibrational spectra of the neutral, cation, and anion species of formula PF_n are presented, in order to aid in the product identification. Several absorptions of PF₄+, PF₃+, and {F₂+ are identified, with only PF₃+ common to both systems. Other prominent absorptions are contributed by PF₅-, PF₄-, and PF₃-. In all of the Ne:PF₅ experiments and some of the Ne:PF₃ experiments, F^3^PO was a major contaminant. Therefore, ab initio calculations were also conducted for most of the neutral and charged species which can result from F^3^PO. There is strong evidence supporting the identification of two of the vibrational fundamentals of F₃PO-, and some evidence for a third. Other tentative assignments are suggested for neutral and charged species derived from F₃PO.

Citation

Journal of Chemical Physics

Volume

108

Pub Type

Journals

Keywords

ab initio calculations, FnPO (n = 1-3), FnPO+ (n = 1, 2), FnPO- (n = 1-4), infrared spectrum, neon matrix, PFn (n = 1-6), PFn+ (n = 1-4), PFn- (n =1-6)

Citation

Lugez, C. , Jacox, M. , King, R. and Schaefer, H. (1998), Experimental and ab Initio Study of the Infrared Spectra of Ionic Species Derived from PF5, PF3 and F3PO and Trapped in Solid Neon, Journal of Chemical Physics (Accessed December 12, 2024)