First-principles study of interaction of cluster Au32 with CO, H2, and O2

Abstract

First-principles calculations are performed to study the interaction of cluster Au 32 with small molecules, such as CO, H 2 , and O 2 . The cagelike Au 32 ( I h ) shows a higher chemical inertness than the amorphous Au 32 ( C 1 ) with respect to the interaction with small molecules CO, H 2 , and O 2 . H 2 can only be physically adsorbed on Au 32 ( I h ) , while it can be dissociatively chemisorbed on Au 32 ( C 1 ) . Although CO can be chemically adsorbed on Au 32 ( I h ) and Au 32 ( C 1 ) with one electron transferred from Au 32 to the antibonding π * orbit of CO, it is bound more strongly on Au 32 ( C 1 ) than on Au 32 ( I h ) . Spin polarized and spin nonpolarized calculations result almost identical ground state structures of Au 32 ( I h ) – O 2 and Au 32 ( C 1 ) – O 2 , in which O 2 is dissociatively chemisorbed.