Time-dependent density functional theory (TD-DFT) is used to assist synthetic catalyst design for solar photoconversion by exploring different ligand and metal complexes. Through characterizing excited states of 1st row transition metal Schiff-base and salen type complexes, periodic trends have been elucidated. The excited states of these complexes were analyzed through generation of theoretical UV-vis absorption spectra and comparison of their respective natural transition orbitals (NTOs). These calculations have been used in coordination with experimental data to design an earth abundant molecular species that will absorb solar radiation and selectively activate C-X π systems. Calculations show that the electron transfer process of the complexes is highly sensitive to both metal and type of ligand. Square planar Zn(II), Cu(II), and Ni(II) macrocyclic salophen type complexes showed adequate absorption in the visible region. Extended conjugation and nitrogen coordination provides enhanced absorption when compared non-planar and oxygen coordinated counterparts. Accordingly, complexes can be tuned through modifications to both metals and ligands to yield promising photocatalytic properties.

Using TD-DFT and NTOs to model photocatalysis

249th National Meeting (2015)

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