Sophia E. Daire

Further investigations of the Ã←X̃ transition of the Kr·NO and Xe·NO complexes using (1+1) REMPI spectroscopy

Abstract The A←X transitions of the Kr·NO and Xe·NO molecular complexes have been recorded with improved quality. In both cases the origin band consists of a single feature, consistent with a (near) linear A state. The spectra demonstrate a wealth of structure, which increases in complexity to higher energy; this is interpreted in terms of a weakening of the interaction as the internal energy increases. Dissociation energies for both the X and A states are derived. Attempts to record the corresponding spectra for Ne·NO were unsuccessful. The trend in the binding energies in the X and A states of Rg·NO (Rg=He–Xe) is discussed.

The à 2Σ+ state of Ar⋅NO

The  2Σ+ state of Ar⋅NO is studied using (1+1) resonance-enhanced multiphoton ionization (REMPI) spectroscopy. Higher quality spectra than obtained in other studies allow the identification of a number of previously unreported features. The spectrum is analyzed using two models: a rigid van der Waals complex in which NO is weakly bonded to Ar; and a complex in which the free internal rotation of NO is hindered by the anisotropy caused by the presence of the Ar atom. It is concluded that as the intermolecular stretch is excited, then the anisotropy decreases, and the angular motion of the complex becomes more and more like that of a free rotor. Near the origin, the complex has an average geometry approaching linear, whereas when the intermolecular stretch is excited, an average geometry closer to T-shaped occurs; however, when the anisotropy is small, the concept of geometry becomes ill-defined.

The Ã←X̃(1+1)REMPI spectrum and high-level ab initio calculations of the complex between NO and N2

The results of two separate studies of the complex between NO and N2 are reported. The (1+1) REMPI spectrum of the A←X transition of the complex between NO and N2 is presented of improved quality over that reported previously, and the appearance of the spectrum is discussed. The results of high-level ab initio calculations [RCCSD(T)/aug-cc-pVQZ//QCISD/6-311+G(2d)] on the X 2Π state are also reported. The indications are that the NO moiety is more freely rotating in the complex than is N2, and that a wide angular space is sampled in the zero-point energy level. The appearance of the REMPI spectrum suggests that the A 2Σ+ state is (close to) linear, and RCCSD(T)//QCISD calculations on the A state, using Rydberg-function-augmented basis sets, suggest that the lowest energy linear isomer is the ON⋅N2 linear orientation. It is clear, however, that the understanding of this complex, and its spectroscopy, is far from complete, and will be challenging.

A theoretical study of the ligand-exchange reactions of Na+ X complexes (X = O, O2, N2, CO2 and H2O): implications for the upper atmosphere

This article has been retracted at the request of the editor. Reason: The publisher regrets that several errors appeared in this paper and that it therefore has been retracted. A correct version of the complete paper has been published in Volume 64, Issue 7, pages 863–870 of the Journal of Atmospheric and Solar-Terrestrial Physics.

Erratum. A theoretical study of the ligand-exchange reactions of Na+·X complexes (X = O, O-2, N-2, CO2 and H2O): implications for the upper atmosphere (vol 64, pg 863, 2002)

This article has been retracted at the request of the editor. Reason: The publisher regrets that several errors appeared in this paper and that it therefore has been retracted. A correct version of the complete paper has been published in Volume 64, Issue 7, pages 863–870 of the Journal of Atmospheric and Solar-Terrestrial Physics.