Coupled-cluster calculations on the C2 molecule and the C+2 and C−2 molecular ions

Abstract

Coupled‐cluster methods including effects of triple excitations have been used with large basis sets to study several electronic states of C₂, C⁻₂, and C⁺₂. r_e, ω_e, D_e, and T_e have been computed for each state considered. For those states for which experimental data are available, the errors are typically less than 0.002 Å, 20 cm⁻¹, and 0.1 eV for r_e, ω_e, and D_e, respectively. These errors are comparable with the best previous results on C₂ and significantly smaller than those for previous calculations on C⁻₂ and C⁺₂. For T_e the results are also satisfactory and comparable with previous work, but some difficulties arise when one or both of the states have considerable multireference character. For two states of C⁺₂ not experimentally characterized, the present data should be sufficiently accurate to be of some assistance to experimental studies. The electron affinity of the ground state of C₂ and the ionization potentials of the ground and first excited states of C₂ have been computed, and particular attention has been given to correlation errors in these quantities. It has been shown that triple excitations significantly decrease the electron affinity. By neglecting or taking insufficient account of triple excitations, some previous calculations were biased towards the anion and obtained fortuitously good agreement with experiment. The correlation error of the present calculations is such that the calculations are slightly biased towards the neutral molecule, but the error is only 0.2 eV. For the ionization potentials, too, triple excitations play an important role. Reasonable agreement with experiment has been achieved by the present calculations. Overall, the present study: (1) underscores the importance of triple excitations; (2) shows the success of single‐reference coupled‐cluster theory in calculating properties of a single state, even when that state has considerable multireference character; and (3) highlights the care which must be taken when comparing different electronic states with these methods when one or both states have considerable multireference character.