W-Band EPR spectra of [{HC(CMeNAr)(2)}Mn](2) (Ar = 2,6-(Pr2C6H3)-Pr-i) have been measured at different temperatures. The spectra show a behavior which is typical for an antiferromagnetically coupled dimer with excited states populating upon increasing temperature. By following the intensity variation of the different features of the spectra with temperature, we attributed different groups of resonances to the S = 1, 2, and 3 states of the dimer. Their corresponding spin Hamiltonian parameters were derived from simulations. The zero-field-splitting parameters measured in this way were D-S=1 = 1.57 cm(-1) and E-S=1 = 0.064 cm(-1), D-S=2 = 0.266 cm(-1) and E-S=2 = 0.0045 cm(-1), and D-S=3 = 0.075 cm(-1) and E-S=3 = 0. On the basis of the molecular structure of the system, we could estimate that zero-field splitting (ZFS) is the result of anisotropic exchange and single-ion anisotropic contributions of similar magnitude (vertical bar D vertical bar approximate to 0.2 cm(-1)). These results allow a deeper insight into the electronic structure of the Mn(I) centers in low-coordination environments, further supporting the electronic structure of Mn(I) to be 4s(1)3d(5), as previously indicated by DFT calculations.