Franck-Condon simulations of the TiO(OH)2ˉ spectrum are shown as red sticks in Figure . The simulations assume all anions are in their vibrational ground state and have the cis-isomeric form. They match the structure in the overview spectrum, including the labelled A peaks, very well, and enable assignment of the A peaks to progressions in totally symmetric vibrational modes of TiO(OH)2. Peak A1 is assigned to the vibrational origin (0 0 0 ), yielding an adiabatic electron affinity of 1.259(4) eV for TiO(OH)2. The peaks spaced by 413 cm -1 (A1, A3, A7, A11) are assigned to the 3 0 𝑛 progression in the Ti-OH symmetric stretch. Additional peaks (A2, A6, A10) are assigned to the 4 0 1 3 0 𝑛 progression involving excitation of the 4 Ti-OH symmetric wag at 413 cm -1 , and several smaller peaks are assigned to excitation of other totally symmetric vibrations.