Pressure effects on the intervalence-transfer electronic absorption band of the mixed-valence Creutz-Taube ion in various media
In this paper the authors present the results of a pressure tuning spectroscopy (PTS) study of the intervalence-transfer (IT) band of the (Cl/sub 5/ x 5H/sub 2/O) salt of the Creutz-Taube ion. They studied this compound in three media: (1) as a crystalline solid, (2) doped in the polyelectrolyte poly(styrenesulfonic acid) (PSS), and (3) in water (D/sub 2/O). In all cases the principal effect of pressure on the IT band was found to be a shift of the band to higher energy. For the microcrystalline sample this shift was approx. 400 cm/sup -1/ over a pressure range from 0.001 to 200 kbar (1 kbar = 986.9 atm). In this same pressure range the blue shift of the IT band for the PSS-doped sample was approx. 600 cm/sup -1/. In water (D/sub 2/O) the shift was approx. 35 cm/sup -1/ in a pressure range from 0.001 to 7 kbar. In addition to the Gaussian fits described above they have fit the spectra using a vibronic coupling model developed by Piepho, Krausz, and Schatz (PKS). When analyzed in terms of this simple small-polaron model, this peak shift corresponds primarily to an increase in the electronic coupling between the metal centers of the ion. The degree of vibronic coupling changes either only slightly or not at all with pressure.
- Research Organization:
- Univ. of Illinois, Urbana (USA)
- DOE Contract Number:
- AC02-76ER01198
- OSTI ID:
- 5100038
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 92:7
- Country of Publication:
- United States
- Language:
- English
Similar Records
Optical probes of interlamellar redox chemistry: intercalation of the Creutz-Taube complex into hydrogen uranyl phosphate. Technical report
Mixed-valence molecular four-dot unit for quantum cellular automata: Vibronic self-trapping and cell-cell response
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHLORINE COMPOUNDS
ELECTRONIC STRUCTURE
PYRAZINES
RUTHENIUM COMPLEXES
COUPLING
EXPERIMENTAL DATA
HEAVY WATER
HYDRATES
POLYSTYRENE
PRESSURE DEPENDENCE
SOLIDS
SULFONIC ACIDS
VIBRATIONAL STATES
AZINES
COMPLEXES
DATA
ENERGY LEVELS
EXCITED STATES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
MATERIALS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PETROCHEMICALS
PETROLEUM PRODUCTS
PLASTICS
POLYMERS
POLYOLEFINS
POLYVINYLS
SYNTHETIC MATERIALS
TRANSITION ELEMENT COMPLEXES
WATER
400201* - Chemical & Physicochemical Properties