Full configuration interaction potential energy curves for the X-1 Sigma(+)(g), B-1 Delta(g), and B-'1 Sigma(+)(g) states of C-2: A challenge for approximate methods

Abstract

The C₂ molecule exhibits unusual bonding and several low-lying excited electronic states, making the prediction of its potential energy curves a challenging test for quantum chemical methods. We report full configuration interaction results for the X 1Σg+, B 1Δg, and B′ 1Σg+ states of C₂, which exactly solve the electronic Schrödinger equation within the space spanned by a 6-31G∗ basis set. Within the D2h subgroup used by most electronic structure programs, these states all have the same symmetry (1Ag), and all three states become energetically close for interatomic distances beyond 1.5 Å. The quality of several single-reference ab initio methods is assessed by comparison to the benchmark results. Unfortunately, even coupled-cluster theory through perturbative triples using an unrestricted Hartree–Fock reference exhibits large nonparallelity errors (>20 kcal mol−1) for the ground state. The excited states are not accurately modeled by any commonly used single-reference method, nor by configuration interaction including full quadruple substitutions. The present benchmarks will be helpful in assessing theoretical methods designed to break bonds in ground and excited electronic states.