Chemisorption of atomic and molecular oxygen on Au and Ag cluster anions: discrimination of different isomers

Structures of coinage metal clusters reacted with atomic and molecular oxygen were studied using Ultraviolet Photoelectron Spectroscopy and Density Functional Theory calculations. We show that O2 partially dissociates on Ag 2 - , and this dissociative chemisorption is a kinetically hindered step. For Au 4 O 2 - , in addition to the previously observed molecularly adsorbed oxygen, we are now able to synthesize a second isomer using atomic oxygen reagents, in which oxygen adsorbs dissociatively. We demonstrate that different isomers can be distinguished by comparative studies of chemisorption of atomic and molecular species on metal clusters, which is otherwise difficult.