First-principles simulation of a photoinduced carbocation formation

► First-principles simulation of the photodissociation of diphenylmethyl chloride. ► Excited-state dynamics described with restricted open-shell Kohn-Sham (ROKS). ► Formation of radicals in the gas phase. ► In aqueous solution ultrafast formation of a carbocation. ► Ion pair formation in two steps: radical-pair formation, electron transfer.