The results of two separate studies of the complex between NO and N 2 are reported. The (1 ϩ1) REMPI spectrum of the à ←X transition of the complex between NO and N 2 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 ͓RCCSD͑T͒/aug-cc-pVQZ//QCISD/6-311ϩG͑2d͔͒ on the X 2 ⌸ state are also reported. The indications are that the NO moiety is more freely rotating in the complex than is N 2 , and that a wide angular space is sampled in the zero-point energy level. The appearance of the REMPI spectrum suggests that the à 2 ⌺ ϩ state is ͑close to͒ linear, and RCCSD͑T͒//QCISD calculations on the à state, using Rydberg-function-augmented basis sets, suggest that the lowest energy linear isomer is the ON•N 2 linear orientation. It is clear, however, that the understanding of this complex, and its spectroscopy, is far from complete, and will be challenging.

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Articles you may be interested inTwo-dimensional laser induced fluorescence spectroscopy of van der Waals complexes: Fluorobenzene-Ar n (n = 1,2) J. Chem. Phys. 136, 134309 (2012); 10.1063/1.3697474Imaging the rotationally state-selected N O ( A , n ) product from the predissociation of the A state of the NO-Ar van der Waals cluster Electronic spectroscopy of the 3 d Rydberg states of NO-Rg ( Rg = Ne , Ar , Kr , Xe ) van der Waals complexesThe à 2 ⌺ ϩ state of Ar•NO is studied using ͑1ϩ1͒ resonance-enhanced multiphoton ionization ͑REMPI͒ 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.