Density functional theory (DFT) calculations on the tetrahedral Mn(VI), Cr(V), and V(IV)(d(1)) oxo anions in their ground and lowest excited d-d and O --> M charge transfer (CT) states are reported and used to assign the electronic absorption spectra by reference to the spectra of the isoelectronic Mn(VII), Cr(VI), and V(V) (d(0)) and the Mn(V) and Cr(IV) (d(2)) anions. Calculated geometrical shifts along the totally symmetric metal-ligand vibration (alpha(1)) for electronic excitations are in agreement with data deduced from experimental vibronic fine structures, supporting the proposed assignments. Using a CT model including (as different from DFT) configuration interaction (CICT), it is shown that the CT excited states of MnO(4)(2)(-) at 17 000, 23 300, and 28 200 cm(-)(1) are due to d(2) (3)A(2)(2e(2)), (1)E(2e(2)), and (3)A(2)(2e(2)) final states combining with a single hole (L) on the ligand 1t(1) and 4t(2) orbitals, respectively. The higher 10Dq and smaller B values for the d(2)L(d(1)) states compared to those of the d(2) systems correlate with the shortening of the metal-ligand bond accompanying the removal of electrons from the antibonding d orbitals, leading to an increase in covalency and a change in the ordering of CT states for Cr(V) with (3)T(2)(2e(1)5t(2)(1))L (10Dq) at a higher energy than (1)E(2e(2))L (8B + 2C) as compared to Cr(IV) with nearly degenerate (3)T(2)(2e(1)5t(2)(1)) and (1)E(2e(2)) terms. This allows one to estimate the energy of the (3)A(2)(2e(2))L --> (1)E(2e(2))L transition from the CT (d(2)L) spectrum of Cr(V)(d(1)), which could not be observed for Cr(IV). From a comparison of calculated and experimental oscillator strengths and Huang-Rhys factors (S) for the lowest CT band in the V(V), Cr(VI), and Mn(VII) (d(0)) and the V(IV), Cr(V), and Mn(VI) (d(1)) oxo anions, it is shown that the increase in covalency from left to right in this series is accompanied by a reduction in band intensity and S for the progression in the alpha(1) vibration. An explanation of this result in terms of ionic contributions to the metal-ligand bond increasing from Mn(VI) to Cr(V) and V(IV) is proposed. Intensities of "d-d" transitions display the opposite trend; increasing covalency leads to stronger mixing between d --> d and CT excited states and thus an increase in intensity.