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9.1: The Magnitude of Molar Absorptivities

  • Page ID
    220467
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    Molar absorptivities,\({\epsilon}\), have units of liters/(mole cm) and range in value from 0 to 105.  The relationship between \({\epsilon}\) and the capture cross-section for a photon - chemical species interaction and the probability for an energy-absorbing transition was shown by Braude (J. Am Chem Soc, 379 (1950) to be 

    \({\epsilon}\) = 8.7 x 1019 PA 

    where P is the transition probability and A is the section target area in units of cm2.  Typical organic molecules have been shown to have cross-sectional areas on the order of 10-15 cm2 and transition probabilities range from 0  to 1. 

    Absorption bands with \({\epsilon}\) ranging from 104 to 105 are considered strong absorbers while absorption bands with \({\epsilon}\) less than or equal to 103 are considered weak absorbers and are likely the results of quantum mechanically forbidden transitions with P < 0.01.

     


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