Appraisal of the performance of nonhybrid density functional methods in characterization of the Al4C molecule

Abstract

In three recent publications it was predicted that an Al(4)C molecule is planar on the basis of nonhybrid density functional calculations. These conclusions contradict our earlier predictions that Al(4)C is tetrahedral. In order to resolve the controversy we probed in this paper a potential energy surface of Al(4)C using a large variety of theoretical methods including multiconfigurational methods and a variety of one-electron basis sets. We confirmed that the nonhybrid Becke's exchange with Perdew-Wang 1991 correlation functional density functional method predicts that Al(4)C has a planar structure in agreement with the reports of the other three groups. However, in this paper we have shown that high level ab initio calculations at the coupled cluster with singles, doubles, and noniterative triples and at the complete active space self-consistent field followed by multireference configurational interaction levels of theory confirm our earlier prediction that Al(4)C is indeed tetrahedral. The failure of nonhybrid density functional methods to correctly characterize the global minimum structure of Al(4)C demonstrates that it is dangerous to rely solely on these density functional methods in characterization of new molecules and clusters, where experimental structure is not known.