Structure and predissociation of the 3p sigma(u)D (3)Sigma(+)(u) Rydberg state of N(2): First extreme-ultraviolet and new near-infrared observations, with coupled-channels analysis

Abstract

The 3p sigma(u)D (3)Sigma(+)(u) Rydberg state of N(2) is studied experimentally using two high-resolution spectroscopic techniques. First, the forbidden D (3)Sigma(+)(u)-X (1)Sigma(+)(g) transition is observed for the first time via the (0,0) band of (14)N(2) and the (1,0) band of (15)N(2), using 1 extreme-ultraviolet +1 ultraviolet two-photon-ionization laser spectroscopy. Second, the Rydberg-Rydberg transition D (3)Sigma(+)(u)-E (3)Sigma(+)(g) is studied using near-infrared diode-laser photoabsorption spectroscopy, thus extending the previous measurements of Kanamori [J. Chem. Phys. 95, 80 (1991)], to higher transition energies, and thereby revealing the (2,2) and (3,3) bands. The combined results show that the D(v=0-3) levels exhibit rapidly increasing rotational predissociation as v increases, spanning nearly four orders of magnitude. The D-state level structure and rotational predissociation signature are explained by means of a coupled-channels model which considers the electrostatically coupled (3)Pi(u) Rydberg-valence manifold, together with a pure-precession L-uncoupling rotational interaction between the 3p sigma(u)D (3)Sigma(+)(u) and 3p pi(u)G (3)Pi(u) Rydberg p-complex components.