Details

Autor(en) / Beteiligte

• Cunningham, Ethan M.
• Gentleman, Alexander S.
• Beardsmore, Peter W.
• Mackenzie, Stuart R.

Titel

Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li, Al) ion-molecule complexes

Ist Teil von

• Molecular physics, 2019-11, Vol.117 (21), p.2990-3000

Ort / Verlag

Abingdon: Taylor & Francis

Erscheinungsjahr

2019

Quelle

Taylor & Francis

Beschreibungen/Notizen

• We present the results of a combined experimental and computational study of the structures of gas-phase M + (N 2 O) n (M = Li, Al) complexes. Infrared spectra were recorded in the region of the N 2 O asymmetric (N = N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M + (N 2 O) n (M = Cu, Ag, Au and M = Co, Rh, Ir) complexes, N- and O-bound isomers in this case are near isoenergetic and are not distinguished spectroscopically at this resolution. In the case of Li + complexes, there is, however, evidence for the presence of bound N 2 moieties, indicating the presence of inserted, OLi + N 2 (N 2 O) n -type structures. The weak N 2 band lies to the blue of the signature of molecularly N- and O-bound ligands and is well-reproduced in the simulated spectra of energetically low-lying structures computed from density functional theory. No such inserted isomers are observed in the case of Al + (N 2 O) n complexes whose infrared spectra can be understood on the basis of molecularly-bound N 2 O ligands. The differences in M + (N 2 O) n structures observed for these closed-shell, ns 2 , metal centres relative to other metal cations are discussed in terms of the likely bonding motifs.