Intensities in the experimental and theoretical spectra are largely governed by Franck-Condon considerations. All peaks below the TS asymptote correspond to transitions in the product well on the neutral PES. The theoretically predicted anion geometry has a notably large HF bond length (1.592Å), akin to that of the TS (1.515 Å) and much larger than that of the PC (0.939 Å). Hence, photodetachment to PClike states should be accompanied by vibrational excitation in the HF stretching mode, resulting in larger FC factors to vibrationally-excited HF products. However, the HF frequency is much larger than the observed peak spacings in the PC region, indicating that there is also considerable excitation of the lowfrequency vibrations of the NH2⋅HF complex. These could arise from the low-frequency NH2⋅HF stretch, analogous to previous cryo-SEVI work on the F + CH3OH reaction that found a series of quasibound vibrational progressions of the CH3O-HF product complex with translational motion along the dissociation coordinate. In addition, the pyramidal structure of NH3 in FNH3ˉ is flattened due to the loss of an H to F, which could lead to excitation of the out-of-plane mode of the FH-NH2 complex. The anion geometry also has good geometric overlap with the neutral TS, leading to structure in the spectrum at higher eBE as discussed in more detail below.