Imaging transient molecular configurations in UV-excited diiodomethane

Femtosecond structural dynamics of diiodomethane (CH2I2) triggered by ultraviolet (UV) photoabsorption at 290 and 330 nm are studied using time-resolved coincident Coulomb explosion imaging driven by a near-infrared probe pulse. We map the dominant single-photon process, the cleavage of the carbon-iodine bond producing rotationally excited CH2I radical, identify the contributions of the three-body (CH2 + I + I) dissociation and molecular iodine formation channels, which are primarily driven by the absorption of more than one UV photon, and demonstrate the existence of a weak reaction pathway involving the formation of short-lived transient species resembling iso-CH2I2-like geometries with a slightly shorter I-I separation compared to the ground-state CH2I2. These transient molecular configurations, which can be separated from the other channels by applying a set of conditions on the correlated momenta of three ionic fragments, are formed within ∼100 fs after the initial photoexcitation and decay within the next 100 fs.