The transition state region of the F + H(2) reaction has been studied by photoelectron spectroscopy of FH(2)(-). New para and normal FH(2)(-)photoelectron spectra have been measured in refined experiments and are compared here with exact three-dimensional quantum reactive scattering simulations that use an accurate new ab initio potential energy surface for F + H(2). The detailed agreement that is obtained between this fully ab initio theory and experiment is unprecedented for the F + H(2) reaction and suggests that the transition state region of the F + H(2) potential energy surface has finally been understood quantitatively.