Electron transfer rates with vibrational state resolution
- Northwestern Univ., Evanston, IL (United States)
Charge transfer excitation at 600 nm of the ion pair [Co(Cp)[sub 2][sup +][vert bar]Co(CO)[sub 4][sup [minus]]] prepares a neutral pair that can undergo spontaneous electron transfer. Electron transfer rates were measured by picosecond transient IR absorption for quantum numbers of 0 and 1 in the CO stretching mode of the Co(CO)[sub 4] species. The rate of electron transfer was 2 times faster with one quantum of energy in the CO stretch mode. The electron transfer returns the ion pair species, and we measured transient IR for levels having 2, 3, and 4 quanta in the ion pair. The rise time of these levels is consistent with the measured rates of leaving the neutral pair. A model calculation was done that shows approximate agreement with the observed ratio of electron transfer rates. This is the first observation of electron transfer rates with vibrational resolution. 27 refs., 3 figs.
- DOE Contract Number:
- FG02-91ER14228
- OSTI ID:
- 6768069
- Journal Information:
- Journal of Physical Chemistry; (United States), Vol. 98:39; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ION PAIRS
EXCITATION
ORGANOMETALLIC COMPOUNDS
ABSORPTION SPECTRA
ELECTRON TRANSFER
INFRARED SPECTRA
VIBRATIONAL STATES
CARBONYLS
CHARGE TRANSPORT
CHEMICAL REACTION KINETICS
COBALT COMPLEXES
CYCLOPENTADIENE
MATHEMATICAL MODELS
QUANTUM NUMBERS
TRANSIENTS
ALKENES
COMPLEXES
CYCLOALKENES
DIENES
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
HYDROCARBONS
KINETICS
ORGANIC COMPOUNDS
POLYENES
REACTION KINETICS
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
661300 - Other Aspects of Physical Science- (1992-)