Abstract
Time-resolved vibrational femtosecond spectroscopy is employed to investigate the photoinduced Wolff rearrangement reaction of diazonaphthoquinone (DNQ) dissolved in different solvents (methanol and water). DNQ is an important compound in commercial Novolak photoresists. Upon photoexcitation the ketene intermediate appears within 300 fs, indicating that the ketene is formed in a very fast concerted process involving N(2) loss and rearrangement. The strong shift of the vibrational band, assigned to the ketene by density functional theory calculations and experimental infrared spectra, toward higher wavenumbers is attributed to vibrational cooling. The relaxation time depends on the solvent (10 ps in methanol and 3 ps in water). However, the spectroscopic data show that the indirect ketene formation via a carbene intermediate might also be involved in the reaction process contributing to the ketene formation on the 10 ps time scale.
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