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- W2983755027 abstract "Abstract Kinetics of thermostimulated luminescence (TSL) of poly(diphenylenephthalide) (PDPh) films has been studied using mathematical modelling and DFT approximation. TSL of PDPh-film was considered to be arising from irradiative deactivation of diphenylene (DP) fragment of polymer chain in excited state formed upon recombination of the spatial separated ion-radical pairs generated by photoexcitation. Two parallel monomolecular transformations leading to excited DP have been revealed: the first path is characterized by the activation parameters of the kinetic rate constant k1 which equal to A1 ≈ 105 sec−1 and Ea1 ≈ 70 kJ mol−1. This path may be interpreted in terms of mechanical relaxation theory by segmental polymer mobility as electron transfer (ET) from phthalide (Ph) anion-to DP cation-radical. The second channel is supposed to be consist of two consecutive ET from triarylmethyl anion-radical to phthalide neutral (A2 ≈ 1 sec−1, Ea2 ≈ 20 kJ mol−1), and then to DP cation-radical (A3 ≈ 104 sec−1, Ea3 ≈ 40 kJ mol−1) of the polymer chain indicating γ- and β-relaxation, respectively. The revealed mechanistic steps and electron retention efficiency estimated in B97-2/6-311 + G(d,p) approximation for the most probable anion-radicals may point out the key role of domino quantum tunneling in transfer and recombination of charges in PDPh films." @default.
- W2983755027 created "2019-11-22" @default.
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- W2983755027 date "2020-02-01" @default.
- W2983755027 modified "2023-10-16" @default.
- W2983755027 title "Thermostimulated luminescence of poly(diphenylenephthalide) films. Kinetics and mechanistic steps of irradiative processes" @default.
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- W2983755027 doi "https://doi.org/10.1016/j.jlumin.2019.116869" @default.
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