Vibrational fine structure in the absorption spectrum of tetrahedra tetroxo complexes: a tddft study

Abstract

Computational studies based on time dependent density functional theory have been conducted to study the excited state structures of the tetroxo d0 transition metal complexes Mn04- , Tc04- , Ru04 and Os04. All the calculations were performed with the ADF 2010 package. It was observed that all the investigated complexes has a C3V geometry for the first excited state. The second excited state has a C2v geometry in case of Mn04- whereas all the other investigated complexes has a D2ct geometry. It was found that the third excited state of Mn04- has a D2ct geometry. Finally, Frank-Condon method was used to simulate the vibronic structure of the absorption spectra of the investigated complexes. The simulated spectra were finally compared with the experimental spectra and results from other theoretical investigations.