title: Structure and predissociation of the 3psigma(u)D (3)Sigma(u) (+) Rydberg state of N(2): first extreme-ultraviolet and new near-infrared observations, with coupled-channels analysis.
abstract: The 3psigma(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 et al. [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 3psigma(u)D (3)Sigma(u) (+) and 3ppi(u)G (3)Pi(u) Rydberg p-complex components.
authors.affiliation: Research School of Physical Sciences and Engineering, The Australian National University, Canberra, Australian Capital Territory, Australia. brenton.lewis@anu.edu.au
authors.forename: B R
authors.initials: BR
authors.lastname: Lewis
authors.forename: K G H
authors.initials: KG
authors.lastname: Baldwin
authors.forename: A N
authors.initials: AN
authors.lastname: Heays
authors.forename: S T
authors.initials: ST
authors.lastname: Gibson
authors.forename: J P
authors.initials: JP
authors.lastname: Sprengers
authors.forename: W
authors.initials: W
authors.lastname: Ubachs
authors.forename: M
authors.initials: M
authors.lastname: Fujitake