Effects of environment of the activated nonradiative decay of the /sup 3/A/sub 2/ state of Rh/sub 2/(TMB)/sub 4//sup 2 +/
The effect of environment on the temperature dependence of the nonradiative decay of the /sup 3/A/sup 2/ state of Rh/sub 2/(TMB)/sub 4//sup 2 +/ (TMB = 2,5-dimethyl-2,5-diisocyanohexane) is studied. The temperature dependence of the observed nonradiative decay rate can be approximately fit to an Arrhenius-like expression: k/sub obsd/ = k/sub 0/ + Ae/sup -E/sub a//RT/. Arrhenius parameters are obtained in seven different environments, with the activation energies varying from 1970 to 3420 cm/sup -1/. A plot of 1n A vs. E/sub a/, known as a Barclay-Butler plot, is linear, with slope = 3.3 x 10/sup -3/ cm and y intercept = 20.0. The linear Barclay-Butler plot suggests that the activated decay from the /sup 3/A/sub 2/ state of Rh/sub 2/(TMB)/sub 4//sup 2 +/ has the same mechanism, regardless of environment. Single-crystal, dilute-plastic, and dilute-crystal environments have been tested. 13 references, 4 figures.
- Research Organization:
- Univ. of California, Santa Cruz
- OSTI ID:
- 5953286
- Journal Information:
- Inorg. Chem.; (United States), Vol. 24:21
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HEXANE
ABSORPTION SPECTROSCOPY
ARRHENIUS EQUATION
RADIATIONLESS DECAY
ORGANIC NITROGEN COMPOUNDS
RHODIUM COMPLEXES
ACTIVATION ENERGY
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
LOW TEMPERATURE
MEDIUM TEMPERATURE
MONOCRYSTALS
POLYMERS
REACTION KINETICS
TEMPERATURE DEPENDENCE
VISIBLE SPECTRA
ALKANES
COMPLEXES
CRYSTALS
DATA
DE-EXCITATION
ENERGY
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EQUATIONS
HYDROCARBONS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)