Femtosecond time-resolved photophysics and photodissociation dynamics of 1-iodonaphthalene

Abstract

The ultrafast relaxation of 1-iodonaphthalene, with particular attention to the dissociation channels, has been studied by time-resolved femtosecond pump–probe mass spectrometry following excitation at 267 and 317 nm. The measured transients for the parent ion and the isobaric fragments, iodine and naphthyl radical, show complex decay profiles with up to four lifetimes in the femto-picosecond time scales. The transients are interpreted as the result of parallel relaxation of the simultaneously excited nσ* and ππ* states of the molecule. While the former leads to dissociation in about 400 fs, the latter converts to lower energy ππ* singlet states at an ultrafast rate (24 fs) followed by intersystem crossing to nearby ππ* triplet states.