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Title: Experimental observation of a very high second electron affinity for ZrF{sub 6} from photodetachment of gaseous ZrF{sub 6}{sup 2{minus}} doubly charged anions

Abstract

The authors report a photodetachment photoelectron spectroscopy study of a doubly charged anion, ZrF{sub 6}{sup 2{minus}}, in the gas phase at two photo energies: 6.424 (193 nm) and 7.865 (157 nm) eV. The adiabatic detachment energy, i.e., the second electron affinity of ZrF{sub 6}, was measured to be extremely high, 2.9(0.2) eV. The vertical detachment energy (VDE) was measured to be 3.4(0.1) eV. Two excited states were also observed for the ZrF{sub 6}{sup {minus}} singly charged anion with VDEs at 4.0 and 4.6 eV, respectively. The repulsive Coulomb barrier, and hence the intramolecular Coulomb repulsion in ZrF{sub 6}{sup 2{minus}}, was estimated from the photon-energy-dependent spectra to be {approximately}2.4 eV. The ZrF{sub 6}{sup 2{minus}} dianion was observed to be metastable with a half-life of {approximately}4 s under the experimental conditions, confirming theoretical predictions that ZrF{sub 6}{sup 2{minus}} is thermodynamically unstable against loss of an F{sup {minus}}, despite its extremely high electronic stability. The authors also performed experiment for the singly charged ZrF{sub 5}{sup {minus}}, but could not observe photodetachment even at 157 nm, the highest photon energy available to us. Thus, the estimated electron affinity of ZrF{sub 5} is larger than 7.8 eV, the highest electron affinity yet confirmed experimentally.

Authors:
;
Publication Date:
Research Org.:
Washington State Univ., Richland, WA (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20075896
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 104; Journal Issue: 19; Other Information: PBD: 18 May 2000; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ZIRCONIUM FLUORIDES; AFFINITY; PHOTOELECTRON SPECTROSCOPY; ANIONS

Citation Formats

Wang, X.B., and Wang, L.S. Experimental observation of a very high second electron affinity for ZrF{sub 6} from photodetachment of gaseous ZrF{sub 6}{sup 2{minus}} doubly charged anions. United States: N. p., 2000. Web. doi:10.1021/jp000362t.
Wang, X.B., & Wang, L.S. Experimental observation of a very high second electron affinity for ZrF{sub 6} from photodetachment of gaseous ZrF{sub 6}{sup 2{minus}} doubly charged anions. United States. doi:10.1021/jp000362t.
Wang, X.B., and Wang, L.S. Thu . "Experimental observation of a very high second electron affinity for ZrF{sub 6} from photodetachment of gaseous ZrF{sub 6}{sup 2{minus}} doubly charged anions". United States. doi:10.1021/jp000362t.
@article{osti_20075896,
title = {Experimental observation of a very high second electron affinity for ZrF{sub 6} from photodetachment of gaseous ZrF{sub 6}{sup 2{minus}} doubly charged anions},
author = {Wang, X.B. and Wang, L.S.},
abstractNote = {The authors report a photodetachment photoelectron spectroscopy study of a doubly charged anion, ZrF{sub 6}{sup 2{minus}}, in the gas phase at two photo energies: 6.424 (193 nm) and 7.865 (157 nm) eV. The adiabatic detachment energy, i.e., the second electron affinity of ZrF{sub 6}, was measured to be extremely high, 2.9(0.2) eV. The vertical detachment energy (VDE) was measured to be 3.4(0.1) eV. Two excited states were also observed for the ZrF{sub 6}{sup {minus}} singly charged anion with VDEs at 4.0 and 4.6 eV, respectively. The repulsive Coulomb barrier, and hence the intramolecular Coulomb repulsion in ZrF{sub 6}{sup 2{minus}}, was estimated from the photon-energy-dependent spectra to be {approximately}2.4 eV. The ZrF{sub 6}{sup 2{minus}} dianion was observed to be metastable with a half-life of {approximately}4 s under the experimental conditions, confirming theoretical predictions that ZrF{sub 6}{sup 2{minus}} is thermodynamically unstable against loss of an F{sup {minus}}, despite its extremely high electronic stability. The authors also performed experiment for the singly charged ZrF{sub 5}{sup {minus}}, but could not observe photodetachment even at 157 nm, the highest photon energy available to us. Thus, the estimated electron affinity of ZrF{sub 5} is larger than 7.8 eV, the highest electron affinity yet confirmed experimentally.},
doi = {10.1021/jp000362t},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 19,
volume = 104,
place = {United States},
year = {2000},
month = {5}
}