Ultrafast events in the electron photodetachment from the hexacyanoferrate(II) complex in solution

Following excitation of the hexacyanoferrate(II) complex in water with a 40 fs laser pulse at 267 nm, the absorption of the hydrated electron rises with a global time constant of 510 fs, whereas the characteristic absorption of the hexacyanoferrate(III) appears almost instantaneously. A transient absorption band around 490 nm is tentatively assigned to the charge-transfer-to-solvent (CTTS) state of the hexacyanoferrate(II). Its ultra-rapid decay (≪60 fs) is due to the electronic repulsion between the electron and its parent core.