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Molecular Physics
An International Journal at the Interface Between Chemistry and Physics
Volume 30, 1975 - Issue 6
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Original Articles

The lowest triplet state of free base porphin

Determination of its kinetics of populating and depopulating from microwave-induced transients in the fluorescence intensity

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Pages 1701-1721 | Received 04 Jun 1975, Published online: 23 Aug 2006
 

Abstract

Transient signals in the fluorescence intensity induced by microwaves can be used to acquire quantitative information on the molecular rates of populating and depopulating of the lowest triplet state of organic molecules. This method seems especially promising when the molecule emits no detectable phosphorescence.

Part of this paper concerns the introduction of an appropriate mathematical model for describing the fluorescence transients. The model is formulated in conjunction with a specific series of experiments from which one may evaluate the molecular quantities in a systematic way. The kinetics of the lowest triplet state of free base porphin (H2P) are determined explicitly by this method.

In the discussion the results for H2P are compared with those for Zn porphin. A satisfactory qualitative explanation based on the theory of radiationless transitions can be given for the great difference in behaviour of these two porphyrin molecules.

Short attention is given to effects due to the photochemical shift of the two H atoms in the centre of H2P, which is proven to occur even at a temperature as low as 1·3 K.

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