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)

Journal Article · Wed Sep 01 04:00:00 EDT 1999 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.479213· OSTI ID:362671

Wang, X; Wang, L ^[1]

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1. Department of Physics, Washington State University, Richland, Washington 99352 (United States)

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.}

• OSTI ID: 362671
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 10 Vol. 111; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
AFFINITY
ANIONS
BINDING ENERGY
ELECTRON DETACHMENT
ELECTRONEGATIVITY
ELECTRONIC STRUCTURE
IRIDIUM CHLORIDES
IRIDIUM COMPOUNDS
OSMIUM CHLORIDES
OSMIUM COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PLATINUM BROMIDES
PLATINUM CHLORIDES
PLATINUM COMPOUNDS
RHENIUM BROMIDES
RHENIUM CHLORIDES
RHENIUM COMPOUNDS