The structure of the nitrous oxide dimer from sub-Doppler resolution infrared spectroscopy

Abstract

The opto-thermal detection method has been used to obtain rotationally resolved infrared spectra for both (14N14N16O)2 and (15N14N16O)2. The vibrational band observed in each case correlates with the ν1+ν3 band of the N2O monomer. A large number of A- and B-type transitions have been assigned and fit for both species yielding accurate molecular constants for both the ground and excited vibrational states. From intensity alternations associated with nuclear spin statistics and the small inertia defect [Δ″=0.611 amu Å2 for (14N14N16O)2], it is clear that the nitrous oxide dimer has a slipped parallel geometry which possesses a center of symmetry. Isotopic substitution shows that of the two such structures, only the one having the oxygen atoms close to one another is experimentally observed. The structural constants are determined to be RNN=3.493(4) Å and θNNO=59.2(5)°.