Classification and quantitative characterisation of the excited states of π-conjugated diradicals

Abstract

Diradicals are of high current interest as emerging materials for next generation optoelectronic applications. To tune their excited-state properties it would be greatly beneficial to have a detailed understanding of the wave functions of the different states involved but this endeavour is hampered by formal and practical barriers. To tackle these challenges, we present a formal analysis as well as concrete results on diradical excited states. We start with a detailed investigation of the avail- able states of a two-orbital two-electron model viewed from, both, the valence-bond and molecular orbital perspectives. We highlight the presence of diradical and zwitterionic states and illustrate their connections to the states found in closed-shell molecules. Subsequently, we introduce practi- cal protocols for analysing states from realistic multireference computations applying these to the paraquinodimethane (pQDM) molecule. The analysis reveals four different categories of states – diradical, zwitterionic, HOMO-SOMO as well as biexciton – while also providing insight into their energetics and optical properties. Twisting the CH2 groups allows us to interconvert between the closed and open-shell forms of pQDM illustrating the connection between the states in both forms. More generally, we hope that this work will lay the foundations for a more powerful rational design approach to diradicals for photophysical applications.