title: 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 (-TR(3)) 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-TR(3) 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 TR(3) 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 time scale.
authors.affiliation: Department of Chemistry, The University of Hong Kong , Pokfulam Road, Hong Kong S.A.R., P. R. China.
authors.forename: Mingyue
authors.initials: M
authors.lastname: Liu
authors.forename: Ming-De
authors.initials: MD
authors.lastname: Li
authors.forename: Jiadan
authors.initials: J
authors.lastname: Xue
authors.forename: David Lee
authors.initials: DL
authors.lastname: Phillips