Electronic Structure Determines Geometry: Bond Length Alternating in Cyclo[2<i>n</i>]carbons

Structure determines the properties. However, whether electronic structure determines geometry or geometry determines electronic structure seems a philosophical question in a chicken and egg situation, which remains unclear. In this work, by applying density functional theory (DFT) and DMRG(4<i>n</i>,4<i>n</i>)-CASSCF methods, theoretical investigation suggested that the dual antiaromaticity in cyclo[2<i>n</i>]carbons with even <i>n</i> should be attributed to the electron correlation effect, instead of decreased geometric symmetry, which actually exists in all cyclo[2<i>n</i>]carbon molecules and does not point out the essence. Such dual antiaromaticity can be conceptualized as electron correlation-stabilized dual antiaromaticity. Results also showed that DFT is reliable for cyclocarbons larger than C₁₄, but we should be careful when applying it to smaller ones. DFT failed to give the correct structure of C₆ compared with density matrix renormalization group results.