First experimental photoelectron spectra of superhalogens and their theoretical interpretations
- Department of Physics, Washington State University, Richland, Washington 99352 (United States)
- Department of Chemistry, The University of Utah, Salt Lake City, Utah 84112 (United States)
Photoelectron spectra of the MX{sub 2}{sup {minus}} (M=Li, Na; X=Cl, Br, I) superhalogen anions have been obtained for the first time. The first vertical detachment energies (VDEs) were measured to be 5.92{plus_minus}0.04 (LiCl{sub 2}{sup {minus}}), 5.86{plus_minus}0.06 (NaCl{sub 2}{sup {minus}}), 5.42{plus_minus}0.03 (LiBr{sub 2}{sup {minus}}), 5.36{plus_minus}0.06 (NaBr{sub 2}{sup {minus}}), 4.88{plus_minus}0.03 (LiI{sub 2}{sup {minus}}), and 4.84{plus_minus}0.06 eV (NaI{sub 2}{sup {minus}}), which are all well above the 3.61 eV electron detachment energy of Cl{sup {minus}}, the highest among atomic anions. Experimental photoelectron spectra have been assigned on the basis of {ital ab initio} outer valence Green function (OVGF) calculations. The corresponding theoretical first VDEs were found to be 5.90 (LiCl{sub 2}{sup {minus}}), 5.81 (NaCl{sub 2}{sup {minus}}), 5.48 (LiBr{sub 2}{sup {minus}}), 5.43 (NaBr{sub 2}{sup {minus}}), 4.57 (LiI{sub 2}{sup {minus}}), and 4.50 eV (NaI{sub 2}{sup {minus}}), in excellent agreement with the experimental values. Photodetachment from the top four valence molecular orbitals (2{sigma}{sub g}{sup 2}2{sigma}{sub u}{sup 2}1{pi}{sub u}{sup 4}1{pi}{sub g}{sup 4}) of MX{sub 2}{sup {minus}} was observed. Analysis of the polestrength showed that all electron detachment channels in this study can be described as primarily one-electron processes. {copyright} {ital 1999 American Institute of Physics.}
- OSTI ID:
- 321466
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 10 Vol. 110; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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