Resonance Raman studies in the extended near infrared region. Experimental verification of a three-site mixing mechanism for valence delocalization in the Creutz-Taube ion
- Northwestern Univ., Evanston, IL (United States)
The Creutz-Taube (C-T) ion, (NH[sub 3])[sub 5]Ru(pyrazine)Ru(NH[sub 3])[sub 5][sup 5+], was among the first intentionally prepared, molecular mixed-valency species. As a prototypical class III (i.e., electronically delocalized) system, it has been the subject of a large number of experimental, as well as theoretical, investigations. While there is now general agreement that features of the ion describe a system exhibiting both ground- and excited-state electronic delocalization, there is significantly less agreement concerning the detailed nature of the delocalization phenomenon. These more specific issues can, however, be resolved by obtaining resonance Raman spectra in the C-T intervalence region (i.e., the extended NIR). We report the first such spectra. From the spectra we find compelling evidence for a three-site mechanism for valence delocalization, necessarily involving extensive, direct bridge orbital participation. 12 refs., 1 fig.
- DOE Contract Number:
- FG02-87ER13808
- OSTI ID:
- 7019646
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:5; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
AMMONIUM COMPLEXES
CHARGED PARTICLES
COMPLEXES
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ENERGY LEVELS
EXCITED STATES
HYDROGEN COMPOUNDS
INFRARED RADIATION
IONS
LASER SPECTROSCOPY
NEAR INFRARED RADIATION
RADIATIONS
RAMAN SPECTROSCOPY
RUTHENIUM COMPLEXES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
VALENCE
VIBRATIONAL STATES