Time-Resolved Spectroscopic and Density Functional Theory Study of the Photochemistry of Irgacure-2959 in an Aqueous Solution

Abstract

The photocleavage reaction mechanism of 2-hydroxy-4´-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure-2959) was investigated using femtosecond (fs) and nanosecond (ns) transient absorption (-TA) spectroscopy and also picosecond (ps) and nanosecond (ns) time-resolved resonance Raman (-TR3) spectroscopy experiments in a water-rich (volume ratio of acetonitrile:water=3:7) solution. TA spectroscopy was used to study the dynamics of the benzoyl radical growth and decay as well as to investigate the radical quenching process by the radical scavenger methyl acrylate. Ps- and ns-TR3 spectroscopies were employed to monitor the formation of the benzoyl radical and also to characterize its electronic and structural properties. The fs-TA experiments results indicate that the Irgacure-2959 lowest lying excited singlet state S1 underwent efficient intersystem crossing (ISC) to convert into its triplet state with a time constant of 4 ps. Subsequently, this triplet species dissociated into the benzoyl and alkyl radicals with a corresponding maximum absorption band at 415 nm. The TR3 results in conjunction with results from DFT calculations confirmed that Irgacure-2959 cleaved into the benzoyl and alkyl radicals at a fast rate on the tens of picosecond timescale. Time-Resolved Spectroscopic and Density Functional Theory Study of the Photochemistry of Irgacure-2959 in an Aqueous Solution (PDF Download Available). Available from: http://www.researchgate.net/publication/264865803_Time-Resolved_Spectroscopic_and_Density_Functional_Theory_Study_of_the_Photochemistry_of_Irgacure-2959_in_an_Aqueous_Solution [accessed Jul 2, 2015].