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Mechanisms of Laser Induced Reactions in Opaque Heterogeneous Environments

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Final technical rept. Nov 1990-Nov 1993

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The technique of laser flash photolysis has been applied to both heterogeneous and homogeneous samples in order to increase understanding of the mechanisms of laser induced reactions at surfaces. Nanosecond diffuse reflectance laser flash photolysis has been used to study triplet state absorption and fluorescence emission of monomers and dimers of acridine orange and other dyes which are shown to aggregate when adsorbed on microcrystalline cellulose and on other surfaces. The properties of excited states within dyed fabrics have been evaluated in several cases. The mechanism of the yellowing of thermomechanical paper pulp has also been investigated and transients studied on nanosecond timescales for the first time. Triplet-triplet energy transfer from benzophenone to oxazine dyes, from eosin to anthracene, and from anthracene to azomethine dyes has been studied on both cellulose and silica surfaces. This work demonstrates the occurrence of energy transfer by static and dynamic mechanisms depending on both the nature of the surface and the adsorbed species. The first picosecond studies exciting directly into the charge transfer absorption bands of aromatic hydrocarbonoxygen complexes formed in the presence of high pressures of oxygen have been carried out to demonstrate the role of charge-transfer interactions in determining the singlet oxygen formation efficiencies during quenching of electronically excited states by molecular oxygen. Nanosecond laser excitation of a series of naphthalene and anthracene derivatives in the presence and absence of oxygen has clearly demonstrated for the first time the importance of charge transfer interactions in determining oxygen quenching constants and singlet oxygen formation efficiencies.

Subject Categories:

  • Organic Chemistry
  • Radiation and Nuclear Chemistry
  • Coatings, Colorants and Finishes

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