LAUSR

Electric dipole moments, polarizabilities, and IR, Raman, optical rotatory dispersion, and electronic and vibrational circular dichroism spectra of the four cis–trans isomers of the proposed [(CO)2(benzoate)FeII/III(terephthalate)CoIII/II(benzoate)(CO)2]+ binuclear complex, having bistablity due to intramolecular charge transfer (IMCT), is investigated using the time-dependent density functional theory ((TD)DFT) B3LYP/6–31G(d,p)[LanL2DZ] method. Results show that the two FeII–CoIII and FeIII–CoII IMCT states of this binuclear complex have distinctly different spectroscopic, optical, and electric response properties, and are sensitive to the cis–trans arrangement of the ligands around the two metallic centres. Furthermore, intrinsic reaction coordinates inter-connecting the two IMCT states are identified using the Duschinsky matrix method. Only one or two of the normal coordinates remain almost (above 80 %) intact during the IMCT reaction which denotes global changes in the bonding strengths and potential energy hypersurface of this bistable binuclear complex. Analysis of the calculated spin densities characterizes the IMCT transition state structures of the trans–trans, cis–cis, and trans–cis isomers as early, early, and late transition states, respectively.