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Title: Photodetachment of free hexahalogenometallate doubly charged anions in the gas phase: [ML{sub 6}]{sup 2{minus}}, (M=Re, Os, Ir, Pt; L=Cl and Br)

Abstract

We report the first observation and photodetachment photoelectron spectroscopic study of a series of hexahalogenometallates dianions MCl{sub 6}{sup 2{minus}} (M=Re, Os, Ir, and Pt) and MBr{sub 6}{sup 2{minus}} (M=Re, Ir, and Pt) in the gas phase. All of these species were found to be stable as free gaseous doubly charged anions. Photoelectron spectra of all the dianions were obtained at several detachment photon energies. The photon-energy-dependent spectra clearly revealed the dianion nature of these species and allowed the repulsive Coulomb barriers to be estimated. The binding energies of the second excess electron in MCl{sub 6}{sup 2{minus}} (M=Re, Os, Ir, Pt) were determined to be 0.46 (5), 0.46 (5), 0.82 (5), and 1.58 (5) eV, respectively, and those in MBr{sub 6}{sup 2{minus}} (M=Re, Ir, Pt) to be 0.76 (6), 0.96 (6), and 1.52 (6) eV, respectively. A wealth of electronic structure information about these metal complexes were obtained and low-lying and highly-excited electronic states of the corresponding singly charged anions were observed. Detachment from metal {ital d} orbitals or ligand orbitals were observed and could be clearly distinguished; detachments from the metal {ital d}-orbitals all occur at low binding energies whereas those from the ligand-dominated orbitals all take place at rathermore » high binding energies. We also found a remarkable correlation between electron affinities measured {ital in vacuo} and the redox potentials obtained in the solution phase of these species. {copyright} {ital 1999 American Institute of Physics.}« less

Authors:
;  [1]
  1. Department of Physics, Washington State University, Richland, Washington 99352 (United States)|[W. R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)
Publication Date:
OSTI Identifier:
362671
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 111; Journal Issue: 10; Other Information: PBD: Sep 1999
Country of Publication:
United States
Language:
English
Subject:
66 PHYSICS; RHENIUM COMPOUNDS; OSMIUM COMPOUNDS; IRIDIUM COMPOUNDS; PLATINUM COMPOUNDS; ANIONS; RHENIUM CHLORIDES; RHENIUM BROMIDES; OSMIUM CHLORIDES; IRIDIUM CHLORIDES; PLATINUM CHLORIDES; PLATINUM BROMIDES; ELECTRON DETACHMENT; PHOTOELECTRON SPECTROSCOPY; ELECTRONIC STRUCTURE; BINDING ENERGY; AFFINITY; ELECTRONEGATIVITY

Citation Formats

Wang, X., and Wang, L. Photodetachment of free hexahalogenometallate doubly charged anions in the gas phase: [ML{sub 6}]{sup 2{minus}}, (M=Re, Os, Ir, Pt; L=Cl and Br). United States: N. p., 1999. Web. doi:10.1063/1.479213.
Wang, X., & Wang, L. Photodetachment of free hexahalogenometallate doubly charged anions in the gas phase: [ML{sub 6}]{sup 2{minus}}, (M=Re, Os, Ir, Pt; L=Cl and Br). United States. doi:10.1063/1.479213.
Wang, X., and Wang, L. Wed . "Photodetachment of free hexahalogenometallate doubly charged anions in the gas phase: [ML{sub 6}]{sup 2{minus}}, (M=Re, Os, Ir, Pt; L=Cl and Br)". United States. doi:10.1063/1.479213.
@article{osti_362671,
title = {Photodetachment of free hexahalogenometallate doubly charged anions in the gas phase: [ML{sub 6}]{sup 2{minus}}, (M=Re, Os, Ir, Pt; L=Cl and Br)},
author = {Wang, X. and Wang, L.},
abstractNote = {We report the first observation and photodetachment photoelectron spectroscopic study of a series of hexahalogenometallates dianions MCl{sub 6}{sup 2{minus}} (M=Re, Os, Ir, and Pt) and MBr{sub 6}{sup 2{minus}} (M=Re, Ir, and Pt) in the gas phase. All of these species were found to be stable as free gaseous doubly charged anions. Photoelectron spectra of all the dianions were obtained at several detachment photon energies. The photon-energy-dependent spectra clearly revealed the dianion nature of these species and allowed the repulsive Coulomb barriers to be estimated. The binding energies of the second excess electron in MCl{sub 6}{sup 2{minus}} (M=Re, Os, Ir, Pt) were determined to be 0.46 (5), 0.46 (5), 0.82 (5), and 1.58 (5) eV, respectively, and those in MBr{sub 6}{sup 2{minus}} (M=Re, Ir, Pt) to be 0.76 (6), 0.96 (6), and 1.52 (6) eV, respectively. A wealth of electronic structure information about these metal complexes were obtained and low-lying and highly-excited electronic states of the corresponding singly charged anions were observed. Detachment from metal {ital d} orbitals or ligand orbitals were observed and could be clearly distinguished; detachments from the metal {ital d}-orbitals all occur at low binding energies whereas those from the ligand-dominated orbitals all take place at rather high binding energies. We also found a remarkable correlation between electron affinities measured {ital in vacuo} and the redox potentials obtained in the solution phase of these species. {copyright} {ital 1999 American Institute of Physics.}},
doi = {10.1063/1.479213},
journal = {Journal of Chemical Physics},
number = 10,
volume = 111,
place = {United States},
year = {1999},
month = {9}
}