Ionic rotational branching ratios in resonant enhanced multiphoton ionization of NO via the A /sup 2/. sigma. /sup +/(3ssigma) and D /sup 2/. sigma. /sup +/(3psigma) states

Journal Article · Thu Jan 14 23:00:00 EST 1988 · J. Chem. Phys.; (United States)

OSTI ID:5596360

Rudolph, H; Dixit, S N; McKoy, V; Huo, W M

We present the results of ab initio calculations of the ionic rotational branching ratios in NO for a (1+1) REMPI (resonant enhanced multiphoton ionization) via the A /sup 2/..sigma../sup +/(3ssigma) state and a (2+1) REMPI via the D /sup 2/..sigma../sup +/(3psigma) state. Despite the atomic-like character of the bound 3ssigma and 3psigma orbitals in these resonant states, the photoelectron continuum exhibits strong l mixing. The selection rule ..delta..N+l = odd (..delta..NequivalentN/sub +/-N/sub i/) implies that the peaks in the photoelectron spectrum corresponding to ..delta..N = odd ( +- 1, +- 3) are sensitive to even partial waves while those corresponding to even ..delta..N probe the odd partial waves in the photoelectron continuum. Recent experimental high resolution photoelectron studies have shown a strong ..delta..N = 0 peak for ionization via the A /sup 2/..sigma../sup +/ and the D /sup 2/..sigma../sup +/ states, indicating a dominance of odd-l partial waves. While this seems natural for ionization out of the 3ssigma orbital, it is quite anomalous for 3psigma ionization. Based on extensive bound calculations, Viswanathan et al. (J. Phys. Chem. 90, 5078 (1986)) attribute this anomaly to a strong l mixing in the electronic continuum caused by the nonspherical molecular potential.

• Research Organization: Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California 91125
• OSTI ID: 5596360
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 88:2; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
BRANCHING RATIO
CHALCOGENIDES
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
IONIZATION
MULTI-PHOTON PROCESSES
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN OXIDES
OXIDES
OXYGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
ROTATIONAL STATES
SPECTROSCOPY