(2 + 1) REMPI spectroscopy of the NO–CO, NO–N₂, and NO–{N₂, Ar} van der Waals complexes in the region of the 4s and 3d Rydberg states

Abstract

We have collected (2 + 1) Resonance-Enhanced Multiphoton Ionization (REMPI) spectra of van der Waals complexes in which a NO molecule is attached to either CO, N(2), or both N(2) and Ar. The energy region probed corresponds to electronic transitions of uncomplexed NO(X(2)Pi) to the 4s and 3d Rydberg states, and we discuss the observed spectra in light of the expected perturbations to these electronic levels induced by complexation. We employ a model in which the van der Waals partners are assumed to reside within the Rydberg orbital, and discuss the importance of core penetration in the description of the electronic structure. By performing calculations on NO(+) interacting with both N(2) and Ar, we identify the global minimum as being a non-planar structure. Further, the N(2) and Ar are found to interact with the NO(+) largely independently, and we find some evidence for this from the REMPI spectrum of NO-{N(2), Ar}.

Anisotropy Measurements from the Near-Threshold Photodissociation of the N2–NO Complex

“…The ground state for the N 2 –NO complex has been extensively studied using both electronic structure calculations and experiments. ,− The overall results for the ground state are consistent with relatively low barriers to internal rotation for the diatomic moieties, resulting in a floppy complex having a minimum geometry with the NO bond approximately perpendicular to the Jacobi vector between the NO center of mass (CM) and N 2 CM. , We henceforth refer to this complex geometry as T-shaped. For the excited state, Lozeille et al performed electronic structure calculations and found nonlinear geometries reverted to the ground state, so only linear excited state geometries were discussed .…”

Photodissociation of the N2-NO Complex between 225.8 and 224.0 nm

“…The Wright group has made several reports on the N 2 -NO complex. ,− Mack et al recorded the (1 + 1) resonance enhanced multiphoton ionization (REMPI) spectrum for the N 2 -NO complex . The REMPI spectrum showed that the N 2 -NO band origin lies 55 cm –1 below free NO.…”

“…Finally, Bergeron et al investigated the (2 + 1) REMPI spectra of the N 2 -NO complex accessed through the 4s and 3d Rydberg states of the NO fragment. The recorded REMPI spectrum of the N 2 -NO complex showed transitions that were assigned to the Ẽ , C̃ , H̃ ′, and F̃ states of the complex …”

“…The recorded REMPI spectrum of the N 2 -NO complex showed transitions that were assigned to the E ̃, C ̃, H ̃′, and F ̃states of the complex. 18 Bartolomei et al measured the velocity-dependent integral scattering cross section for NO and N 2 . 19 The ground-state complex geometry was found using B3LYP/aug-cc-pVQZ calculations, which served as a starting point for the potential energy surface used to fit the integral cross section.…”