Theoretical study on spin-forbidden transitions of osmium complexes by two-component relativistic time-dependent density functional theory

Abstract

We study spin-forbidden transitions of Os polypyridyl sensitizers by two-component relativistic time-dependent density functional theory with the spin–orbit interaction based on Tamm–Dancoff approximation. The absorption spectra, including spin-forbidden-transition peaks, for the Os complexes are reasonably reproduced in comparison with the experimental ones. The extension of the conjugated lengths in the Os complexes is investigated and found to be effective to enhance photo absorption for spin-allowed transitions as well as spin-forbidden ones. This study provides fruitful information for a design of new dyes in terms of conjugation lengths.