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Determining the Extent of Delocalization in Mixed-Valence Iron Dimers using X-ray Absorption Spectroscopy

Journal Article · · Submitted to Journal of Undergraduate Studies
OSTI ID:919425

This study examines the extent of charge delocalization in mixed valence compounds. Understanding the structure of charge delocalization is the first step in understanding the local dynamics of charge transfer. This insight has diverse applications such as the ability to mimic biological reactions and to enhance solar technology. Because of its fast time scale, synchrotron radiation was used to probe the iron K-edge for three organometallic systems. In these complexes, two bridged metal atoms share an effective charge of 5+. In a Robin-Day Class II compound, charge is localized and the two iron atoms have effective oxidation states of 2+ and 3+ respectively. For Class III delocalized compounds each metal center has an effective charge of 2.5+. Class II/III compounds exhibit characteristics of both localized and delocalized systems according to various optical spectroscopies. Synchrotron radiation was used to study charge distribution in these poorly-understood Class II/III intermediate systems. In the limit of absolute localization, spectra of the mixed valence species were expected to be a linear combination of the reduced and oxidized species. For the delocalized case, a linear combination was not expected. These two cases were used as calibration limits to determine the extent of delocalization in the unknown Class II/III compound. Results showed that synchrotron radiation classifies the Class II/III compound as localized. However, data also demonstrated that the linear combination model did not hold as expected and a revised model is necessary to better understand this phenomenon.

Research Organization:
Stanford Linear Accelerator Center (SLAC)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC02-76SF00515
OSTI ID:
919425
Report Number(s):
SLAC-TN-07-025
Journal Information:
Submitted to Journal of Undergraduate Studies, Journal Name: Submitted to Journal of Undergraduate Studies
Country of Publication:
United States
Language:
English

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