The UV absorption spectrum of the permanganate anion is a prototype transition-metal complex spectrum. Despite this being a simple d(0) T-d system, for which a beautiful spectrum with detailed vibrational structure has been available since 1967. the assignment of the second and third bands is still very controversial. The issue can be resolved only by an elucidation of the intricate vibronic structure of the spectrum. We investigate the vibronic coupling by means of linear-response time-dependent density functional calculations. By means of a diabatizing scheme that employs the transition densities obtained in the TDDFT calculations in many geometries around R,, we construct a Taylor series expansion in the normal coordinates of adiabatic potential energy matrix, coupling 24 excited states. The simulated vibronic structure is in good agreement with the experimental absorption spectrum after the adjustment of some of the calculated vertical excitation energies. The peculiar blurred vibronic structure of the second band, which is a very distinctive feature of the experimental spectrum, is fully reproduced in the calculations. It is caused by the double-well shape of the adiabatic energy surface along the Jahn-Teller active e mode of the allowed E-1 state arising from the second IT, state, which exhibits a Jahn-Teller splitting into 1132 and E-1 states. We trace the double-well shape to an avoided crossing between two diabatic states with different orbital-excitation character. The crossing can be explained at the molecular orbital level from the Jahn-Teller splitting of the set of 7t(2){3d(xy), 3d(xz), 3d(yz)} orbitals (the LUMO + 1), to which the excitations characterizing the diabatic states take place. In contrast to its character in the two well regions. at R, the 2(1)T(2) state is not predominantly an excitation to the LUMO + 1, but has more HOMO - 1 --> LUMO (2e = {3dx(2)-x(2), 3d(z)(2)) character. The changing character of the 2(1)T(2) - E-1 state along the e mode implies that the assignment of the experimental bands to single orbital transitions is too simplistic intrinsically. This spectrum. and notably the blurring of the vibronic structure in the second band, can be understood only from the extensive configurational mixing and vibronic coupling between the excited states. This solves the long-standing assignment problem of these bands.