The role of atomic excited states of Au on N2O capture and activation: A multireference second-order perturbation theory study

Abstract

Nitrous oxide (N(2)O) is an intermediate compound formed during catalysis occurring in automobile exhaust pipes. Atomic Au in its ground state is unable to react with N(2)O, however, several Au excited states are bound to N(2)O, but not all of these states are able to activate N(2)O bonds. In this work, N(2)O capture and activation by a single Au atom are studied considering Au in the ground and excited states with multiplicities = 2, 4 and 6. The Au + N(2)O reactions are studied at multireference second-order perturbation level of theory using C(s) symmetry. The AuN(2)O ((4)A', (4)A'', (6)A' and (6)A'') adducts are spontaneously created from Au excited states. From these complexes, only the (4)A', (6)A' and (6)A'' states exhibit N(2)O activation reaction paths yielding N(2,) NO and O atoms as end products when N(2)O approaches Au excited states side-on. Cations both ground and excited states, capture N(2)O although only the Au(+) ((5)A') + N(2)O ((1)Σ(+)) → NAuNO(+) ((5)A') reaction (for the end-on and side-on approaches) shows N(2)O activation with N-N bond breaking. In the case of Au anions, the ground state and most of the excited states capture N(2)O and activation takes place according to Au(-) ((3)A', (5)A', (5)A'') + N(2)O ((1)Σ(+)) → AuO(-) ((3)A', (5)A', (5)A'') + N(2)(g) for the N(2)O end-on approach by the oxygen atom. The reaction paths show a metal-gas dative covalent bonding character. Mulliken charge population analysis obtained for the active states shows that the binding is done through charge donation and retro-donation between the metal and the N(2)O molecule.