Reference Energies for Cyclobutadiene: Automerization and Excited States.

Cyclobutadiene is a well-known playground for theoretical chemists and is particularly suitable to test ground- and excited-state methods. Indeed, due to its high spatial symmetry, especially at the square geometry but also in the rectangular arrangement, the ground and excited states of cyclobutadiene exhibit multiconfigurational characters and single-reference methods, such as standard adiabatic time-dependent density-functional theory (TD-DFT) or standard equation-of-motion coupled cluster (EOM-CC), are notoriously known to struggle in such situations. In this work, using a large panel of methods and basis sets, we provide an extensive computational study of the automerization barrier (defined as the difference between the square and rectangular ground-state energies) and the vertical excitation energies at and equilibrium structures. In particular, selected configuration interaction (SCI), multireference perturbation theory (CASSCF, CASPT2, and NEVPT2), and coupled-cluster (CCSD, CC3, CCSDT, CC4, and CCSDTQ) calculations are performed. The spin-flip formalism, which is known to provide a qualitatively correct description of these diradical states, is also tested within TD-DFT (combined with numerous exchange-correlation functionals) and the algebraic diagrammatic construction [ADC(2)-s, ADC(2)-x, and ADC(3)]. A theoretical best estimate is defined for the automerization barrier and for each vertical transition energy.