Resonance enhanced multiphoton ionization and zero electron kinetic energy spectroscopy of the DABCO–N2 van der Waals complex: Divergent energy level spacings as evidence for an offset parallel structure

Abstract

The DABCO–N2 van der Waals complex has been investigated using a combination of (1+1′) resonance enhanced multiphoton ionization and zero electron kinetic energy spectroscopy, supported by ab initio molecular orbital calculations. The observation of extended vibrational progressions of low wave number with diverging vibrational spacings supports an assignment to an offset parallel structure analogous to the 45° canted parallel structures proposed for the nitrogen dimer. The active vibrational mode is assigned to a mixed van der Waals stretch/rocking mode in which the nitrogen solvent undergoes a hindered rotational motion against the DABCO framework in the plane containing the C3 axis in DABCO and the intermolecular axis in N2. The results of counterpoise corrected ab initio calculations support this assignment to the extent that they suggest that a parallel structure is the most stable with a cross structure identified as a transition state. No experimental evidence is found for the existence of other stable structures.