Rotationally resolved zero-kinetic-energy photoelectron spectrum of nitrogen

Journal article

Rotationally resolved zero-kinetic-energy (ZEKE) photoelectron spectra of the X^2 Σ_(g)^(+) (V^(+) = 0,1)← X^(1)Σ_(g)^(+) (v=0) bands of nitrogen have been recorded. The spectra show unexpected rotational-line intensities. The intensity distortions are explained by channel interactions. The strong S and U branches [N^(+) 0 J^(primeprime)) = +2 and +4, respectively] of the (1-0) band borrow intensity from a nearly degenerate Rydberg state, converging to an electronic excited state of the ion, by a complex resonance mechanism. Field-induced rotational autoionization is shown to enhance the O branch and M branch [N^(+) 0 J^(primeprime)) = -2 and -4] intensity of the (O-O) band. Recording ZEKE spectra with extraction fields of 10-100V/cm appears to be an attractive and powerful way of obtaining spectroscopic information on Rydberg states with simultaneously high principal quantum number n and high total-angular-momentum quantum number J.

Authors: Merkt, F; Softley, T

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Physical Society
• Journal: Physical Review A
• Volume: 46
• Issue: 1
• Pages: 302-314
• Publication date: 1992-07-01
• Edition: Publisher's version
• DOI: 10.1103/PhysRevA.46.302
• EISSN: 1094-1622
• ISSN: 1050-2947
• Language: English
• Subjects: Chemistry & allied sciences; Physical & theoretical chemistry