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Photophysics and kinetics of naphthopyran derivatives, Part 5: An analytical model utilizing temperature effects to evaluate ABC(2k,3–5ϕ) kinetic parameters
Author(s) -
Maafi M.,
Brown R. G.
Publication year - 2007
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20251
Subject(s) - chemistry , absorbance , kinetics , kinetic energy , thermodynamics , reaction rate constant , quantum , thermal , statistical physics , photostationary state , extinction (optical mineralogy) , computational chemistry , organic chemistry , classical mechanics , quantum mechanics , chromatography , physics , catalysis , mineralogy , photoisomerization , isomerization
A theoretical model is established for a photochemical ABC(2k,6ϕ) system in order to characterize the relationship of its absorbance at the photostationary state with temperature. Provided that the thermal processes of the system are not opposing steps, it has been found that depending on the relative magnitude of the system parameters (two rate constants, up to six quantum yields, and two extinction coefficients), several behaviors are predicted by the model. However, from an analytical viewpoint, this mathematical description generates for all cases, six new equations involving kinetic and spectroscopic parameters that are numerically defined by the available experimental data. For the first time, the latter are used to solve the dynamics of several systems. Novel procedures allowing a complete analytical elucidation of ABC(2k,3ϕ) systems (eight unknowns) as well as many other cases belonging to ABC(2k,4–5ϕ) kinetics have been successfully established. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 472–479, 2007