title: Coupling of electron orbital motion with rotation in the high Rydberg states of BH.
abstract: We have applied optical-optical-optical triple resonance spectroscopy to resolve a system of high Rydberg states in BH that serves quantitatively to characterize a fundamental example of electron-orbital-cation core rotational coupling. The third-color ionization-detected absorption spectrum originating from the photoselected 3s B1Sigma+ Rydberg state with vibrational and total angular momentum quantum numbers, v'=1 and N'=0 consists entirely of vibrationally autoionizing resonances for which final N=1 that converge in series to the BH+v+=1 rotational limits, N+=0, 1, and 2. For series with l=1 converging to N+=0 and 2, Rydberg orbital and rotational angular momenta couple to systematically perturb level energies and distribute lifetime in a well-isolated two-channel rotronic interaction that spans hundreds of wave numbers.
authors.affiliation: Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA.
authors.forename: A T
authors.initials: AT
authors.lastname: Gilkison
authors.forename: C R
authors.initials: CR
authors.lastname: Viteri
authors.forename: E R
authors.initials: ER
authors.lastname: Grant