The diradicaloid electronic structure of dialumenes: a benchmark study at the Full-CI limit.

Multiply-bonded main group compounds of groups 13-15 are attracting significant interest not only because they provide fundamental insight into the nature of metal-metal bonding, but also for their potential in small molecule bond activation and catalysis. This includes dialumenes, neutral Al(I) compounds that contain AlAl double bonds, which display high reactivity owing to their intrinsic diradicaloid character. The electronic structure of the simplest dialumene, Al ₂ H ₂ , is here analyzed up to a practical Full-CI limit using DMRG and selected CI methods for the bond dissociation energy (BDE), geometry and properties of the electron density (difference density, ELF). Acquiring Full-CI reference values for the simplest dialumene (but possessing the highest diradical character) allows for a rigorous benchmarking of simpler correlated wavefunction theory (WFT) methods and density functional methods in treating the electronic structure of such systems. Single-reference coupled cluster theory using a RHF reference is found to reliably converge to the Full-CI limit and CCSD(T) is fully capable of capturing the diradical character, while multi-reference methods offer no clear advantages. Density functional methods struggle to fully describe the electronic structure complexity although non-hybrid functionals such as TPSS come close. Solving the inverse Kohn-Sham problem for a Full-CI-quality density revealed minimal density-driven errors in the TPSS-calculated BDE unlike high-percentage hybrids such as M06-2X. No density functional, however, predicts accurate relative energies. Fractional-occupation density plots at the TPSS level correlate well with WFT-based diradical character metrics, a useful result for determining diradical character in larger systems.