Ground and low-lying excited state potential energy surfaces of diiodomethane in four dimensions

Abstract

We report a set of adiabatic potential energy surfaces (PESs) for diiodomethane, including the ground electronic state and all excited states accessible via single-photon absorption near 260 nm. Although constrained to four dimensions, these PESs capture the essential photochemical processes following photoexcitation—namely, bond breaking and rearrangement among the methyl radical and the two iodine atoms. Constructed using an accurate and efficient spline interpolation algorithm, the PESs reproduce local features with high fidelity and exhibit overall smooth first-order derivatives, making them suitable for molecular dynamics simulations. We identify key stationary points on the ground-state PES and on three excited-state PESs, and map reaction pathways leading to CH2I + I dissociation via the intermediate formation of a CH2I–I isomer. These PESs provide a valuable resource for molecular dynamics studies, enabling detailed exploration of photochemistry in diiodomethane.