On The Electronic Structure of[1Fe] Fe-S Complexes From Anionic Photoelectron Spectroscopy

Journal Article · Fri Mar 21 04:00:00 EST 2003 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp027118h· OSTI ID:15005245

Yang, Xin; Wang, Xue B; Fu, Youjun; Wang, Lai S

The electronic structure of a series of Fe-S complexes, Fe(SCN)(3)(-), Fe(SCN)(4)(-), Na+[Fe(SCN)(4)(2-)], Fe(SCH3)(3)(-), Fe(SCH3)(4)(-), Na+[Fe(S-2-o-xyl)(2)(2-)], and Fe(S-2-o-xyl)(2)(-) (where S-2-o-xyl= o-xylene-alpha,alpha'- dithiolate), was investigated in the gas phase using photodetachment photoelectron spectroscopy. Spectral features due to detachment from metal d orbitals or ligand orbitals were distinguished by comparing with the spectrum of a d(0) complex, Sc(SCN)(4)(-). A weak threshold feature was observed in the spectra of all ferrous complexes due to detachment of the minority spin Fe 3d electron[Fe-II (3d(6)) --> Fe-III (3d(5))]. The spin majority Fe 3d electron signals were observed at much higher binding energies, revealing directly the''inverted level scheme'' for these[1Fe] Fe-S complexes based on previous spin polarized calculations. The''inverted level scheme'' is shown to be a general feature of the electronic structures of the[1Fe] Fe-S complexes, independent o f the oxidation state and coordination number. Information about the gas-phase redox potentials and reorganization energies upon oxidation of the ferrous complexes is obtained from the adiabatic and vertical detachment energies of the minority Fe 3d electron.

• Research Organization: Pacific Northwest National Lab., Richland, WA (US), Environmental Molecular Sciences Laboratory (US)
• Sponsoring Organization: US Department of Energy (US)
• DOE Contract Number: AC06-76RL01830
• OSTI ID: 15005245
• Report Number(s): PNNL-SA-39723; 2231; KP1301030
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 11 Vol. 107; ISSN 1089-5639
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
COORDINATION NUMBER
ELECTRONIC STRUCTURE
ENERGY LEVELS
ENVIRONMENTAL MOLECULAR SCIENCES LABORATORY
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IRON COMPLEXES
IRON SULFIDES
OXIDATION
PHOTOELECTRON SPECTROSCOPY
REDOX POTENTIAL
SPIN
THIOCYANATES
VALENCE