Interactions of the 3pπᵤc¹Πᵤ(v=2) Rydberg-complex member in isotopic N₂

Abstract

The 3pπᵤc¹Πᵤ−X¹Σg⁺(2,0)Rydberg and b′¹Σᵤ⁺−X¹Σg⁺(7,0) valence transitions of ¹⁴N₂, ¹⁴N¹⁵N, and ¹⁵N₂ are studied using laser-based 1 extreme ultraviolet (XUV)+1′UV two-photon-ionization spectroscopy, supplemented by synchrotron-based photoabsorption measurements in the case of ¹⁴N₂. For each isotopomer, effective rotational interactions between the c(v=2) and b′(v=7) levels are found to cause strong Λ-doubling in c(v=2) and dramatic P∕R-branch intensity anomalies in the b′−X(7,0) band due to the effects of quantum interference. Local perturbations in energy and predissociation line width for the c(v=2)Rydberg level are observed and attributed to a spin-orbit interaction with the crossing, short-lived C³Πᵤ(v=17) valence level. Show more