Recapture of the Nonvalence Excess Electron into the Excited Valence Orbital Leads to the Chemical Bond Cleavage in the Anion

The excess electron in the dipole-bound state (DBS) of the anion is found to be recaptured into the excited valence orbital localized at the positive end of the dipole, leading to the chemical bond cleavage of the anion. In the DBS of the 4-iodophenoxide anion, the extremely loosely bound electron (binding energy of 53 cm–1) is recaptured into the πσ* valence orbital, which is repulsive along the C–I bond extension coordinate, leading to the...