Developing fast, accurate and spin pure calculations of organic diradical electronic structure

Abstract

Organic diradical molecules have emerged in recent years as highly promising candidates for next generation optoelectronic and quantum information technologies. As efforts continue to synthesise diradicals with unique photophysical properties, developing our theoretical understanding of their complex electronic structure is crucial to enable rational design strategies. However, existing computational tools struggle to properly describe the multi-reference character of diradical electronic states while also preserving a low computational scaling that enables fast calculations on large emissive diradicals. This work presents a new computational method, termed Diradical Extended Restricted Open-shell PPP (D-ExROPPP) theory, which we show yields accurate and spin-pure electronic states at a very low computational cost relative to existing approaches. This is achieved by implementing a novel, spin-adapted configuration interaction approach within the semi-empirical Pariser-Parr-Pople framework. D-ExROPPP is then used to study the electronic structure of three prototypical organic diradicals, and benchmarked against results from computationally intensive, post-Hartree-Fock methods. Excitation energies for these molecules are predicted that show a similar level of accuracy as high-level ab-initio calculations, while requiring up to five orders of magnitude less computational time. We further apply D-ExROPPP to a number of recently reported stable, emissive, organic diradicals. In the majority of cases, electronic transitions measured in experimental UV-vis spectra are reproduced with qualitative accuracy and the spin states involved can be reliably assigned. Together, these results establish D-ExROPPP as a promising new tool for efficiently predicting and interpreting the photophysics of organic diradical molecules.