Quantum-interference effects in the o(1)Pi(u)(v=1)similar to b(1)Pi(u)(v=9) Rydberg-valence complex of molecular nitrogen
2007 (English)In: Molecular Physics, ISSN 0026-8976, E-ISSN 1362-3028, Vol. 105, no 11-12, 1543-1557 p.Article in journal (Refereed) Published
Two distinct high-resolution experimental techniques, 1 XUV + 1 ' UV laser-based ionization spectroscopy and synchrotron-based XUV photoabsorption spectroscopy, have been used to study the o(1) Pi(u)(v =) 1 similar to b(1)Pi(u)(v=9) Rydberg-valence complex of N-14(2), providing new and detailed information on the perturbed rotational structures, oscillator strengths, and predissociation linewidths. Ionization spectra probing the b '(1)Sigma(+)(u)(v= 6)state of N-14(2), which crosses o(1)Pi(u)(v=1) between J = 24 and J = 25, and the o(1)Pi(u)(v= 1), b(1)Pi(u)(v= 9), and b '(1)Sigma(+)(u)(v= 6) states of (NN)-N-14-N-15, have also been recorded. In the case of N-14(2), rotational and deperturbation analyses correct previous misassignments for the low-J levels of o(v=1) and b(v= 9). In addition, a two-level quantum-mechanical interference effect has been found between the o-X(1, 0) and b-X(9, 0) transition amplitudes which is totally destructive for the lower-energy levels just above the level crossing, making it impossible to observe transitions to b(v=9, J=6). A similar interference effect is found to affect the o(v=1) and b(v=9) predissociation linewidths, but, in this case, a small non-interfering component of the b(v= 9) linewidth is indicated, attributed to an additional spin - orbit predissociation by the repulsive 3(3)Sigma(+)(u) state.
Place, publisher, year, edition, pages
2007. Vol. 105, no 11-12, 1543-1557 p.
predissociation, perturbation, diatomic molecules, extreme ultraviolet, laser spectroscopy
IdentifiersURN: urn:nbn:se:kth:diva-37298DOI: 10.1080/00268970701291750ISI: 000249780600008ScopusID: 2-s2.0-34948872035OAI: oai:DiVA.org:kth-37298DiVA: diva2:432937