Theoretical studies of O2−:(H2O)n clusters

Abstract

AbstractThe interaction of superoxide ion O2− with up to four water molecules [O2−: (H2O)n, n = 1, 2, 4] has been investigated using ab initio molecular orbital theory. The binding energy of O2−: H2O is calculated to be −20.6 kcal/mol in good agreement with gas phase experimental data. At the MP3/6‐31G* level the O2−:H2O complex has a C2v structure with a double (cyclic) hydrogen bond between O2− and H2O. A Cs structure with a single hydrogen bond is only 0.7 kcal/mol less stable. Interaction of H2O with the doubly occupied π* orbital of O2− is preferred slightly over interaction with the singly occupied π* orbital. Natural bond orbital analysis suggests that both electrostatic and charge transfer interactions are important in anionic complexes. The charge transfer occurs predominantly in the O2− → H2O direction and is important in determining the relative stabilities of the different structures and states. Singly and doubly hydrogen‐bonded structures for the O2−: (H2O)2 and O2−: (H2O)4 clusters were found to be similar in stability and the increase in binding of the cluster becomes smaller as each additional water molecule is added to the cluster.