Reference Energies for Cyclobutadiene: Automerization and Excited States

TL;DR

This study provides comprehensive reference energies for cyclobutadiene's automerization barrier and excited states using diverse high-level computational methods, addressing challenges posed by its multi-configurational nature.

Contribution

It offers the first extensive benchmark of ground and excited-state energies of cyclobutadiene using multiple advanced computational techniques, including configuration interaction, multi-reference perturbation, and coupled-cluster methods.

Findings

Identified the most accurate computational approaches for automerization barrier

Provided benchmark vertical excitation energies at key geometries

Highlighted limitations of single-reference methods for this system

Abstract

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 $D_{4h}$ square geometry but also in the $D_{2h}$ rectangular arrangement, the ground and excited states of cyclobutadiene exhibit multi-configurational characters and single-reference methods, such as adiabatic time-dependent density-functional theory (TD-DFT) or 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 $D_{2h}$ and $D_{4h}$ equilibrium structures. In particular, selected configuration interaction (SCI), multi-reference 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)] schemes. A theoretical best estimate is defined for the automerization barrier and for each vertical transition energy.