Volume 115, 2000
From the journal:

Faraday Discussions

Ion-pair formation observed in a pulsed-field ionization photoelectron spectroscopic study of HF

Andrew J. Yencha,a   M. Cristina A. Lopes,b   George C. King,*c   Majdi Hochlaf,d   Yang Songe  and  Cheuk-Yiu Nge  

* Corresponding authors

a Department of Chemistry, State University of New York at Albany, Albany, NY, USA

b Departamento de Fisica, ICE, Universidade Federal de Juiz de Fora, Juiz de Fora—MG, Brazil

c Department of Physics and Astronomy, Schuster Laboratory, Manchester University, Manchester, UK
E-mail: GCK@fs3.ph.man.ac.uk

d Theoretical Chemistry Group, Université de Marne-la-Vallée, Champs-sur-Marne, France

e Ames Laboratory, USDOE and Department of Chemistry, Iowa State University, Ames, IA, USA

Abstract

The pulsed-field ionization (PFI) photoelectron (PE) spectrum of HF has been recorded at the chemical dynamics beamline of the advanced light source over the photon energy range 15.9–16.5 eV using a time-of-flight selection scheme at a resolution of 0.6 meV. Rotationally-resolved structure in the HF+(A 2Π3/2,1/2, v+=0, 1) band systems are assigned. The spectral appearance of these systems agrees with a previous VUV laser PFI-PE study. Importantly, extensive rotationally-resolved structure between these two vibrational band systems is also observed. This is attributed to ion-pair formation via Rydberg states converging on the v+=1 vibrational levels of the HF+(A 2Π3/2,1/2) spin–orbit states. These Rydberg states are assigned to the 1Σ+ part of the nd-complexes (σ, π and δ). Ion-pair formation is observed in this study by the detection of F− ions. Some partially rotationally-resolved structure in a previously published threshold photoelectron spectrum is similarly attributed to ion-pair formation (F− detection) through a combination of the v+=17 level of the (A 2Σ+) 3sσ Rydberg state and the (A 2Π3/2,1/2 , v+=1) 7d Rydberg states. On the basis of the present study, an accurate experimental value for the dissociation energy of the ground state of HF has been obtained, D0(HF)=5.8650(5) eV.

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Article information

DOI
https://doi.org/10.1039/A909277C
Article type
Paper
Submitted
24 Nov 1999
First published
31 Mar 2000

Faraday Discuss., 2000,115, 355-362

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Ion-pair formation observed in a pulsed-field ionization photoelectron spectroscopic study of HF

A. J. Yencha, M. C. A. Lopes, G. C. King, M. Hochlaf, Y. Song and C. Ng, Faraday Discuss., 2000, 115, 355 DOI: 10.1039/A909277C

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