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We present the results of a combined experimental and computational study of the structures of gas-phase M+(N2O)n (M = Li, Al) complexes. Infrared spectra were recorded in the region of the N2O asymmetric (N = N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M+(N2O)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 N2 moieties, indicating the presence of inserted, OLi+N2(N2O)n–type structures. The weak N2 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+(N2O)n complexes whose infrared spectra can be understood on the basis of molecularly-bound N2O ligands. The differences in M+(N2O)n structures observed for these closed–shell, ns2, metal centres relative to other metal cations are discussed in terms of the likely bonding motifs. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics of Xe2 Rydberg states in the 76,900–80,000 cm−1 region have been studied using a combination of resonance enhanced multi-photon ionization and velocity map imaging. By monitoring photodissociation product channels as a function of excitation energy, several localized and long range perturbations of the excited states have been identified. In addition, several new band systems have been observed and assigned as the Xe2 5d 2[1/2]0°  ← X , 5d 2[1/2]1°  ← X , 5d 2[3/2]2°  ← X , and 5d 2[7/2]3°  ← X transitions. [ABSTRACT FROM AUTHOR]