Pressure effects on the intervalence-transfer electronic absorption band of the mixed-valence Creutz-Taube ion in various media

Journal Article · Thu Apr 07 04:00:00 EDT 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100318a015· OSTI ID:5100038

Hammack, W S; Lowery, M D; Hendrickson, D N; Drickamer, H G

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), Journal Name: J. Phys. Chem.; (United States) Vol. 92:7; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AZINES
CHLORINE COMPOUNDS
COMPLEXES
COUPLING
DATA
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HEAVY WATER
HETEROCYCLIC COMPOUNDS
HYDRATES
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
POLYSTYRENE
POLYVINYLS
PRESSURE DEPENDENCE
PYRAZINES
RUTHENIUM COMPLEXES
SOLIDS
SULFONIC ACIDS
SYNTHETIC MATERIALS
TRANSITION ELEMENT COMPLEXES
VIBRATIONAL STATES
WATER