Aufsatz in einer Fachzeitschrift
Neutral dissociation of the I, I', and I" vibronic progressions of O₂
Details zur Publikation
Autor(inn)en: | Demekhin, P.; Sukhorukov, V.; Schmoranzer, H.; Ehresmann, A. |
Publikationsjahr: | 2010 |
Zeitschrift: | The Journal of Chemical Physics |
Seitenbereich: | 204303 |
Jahrgang/Band : | 132 |
ISSN: | 0021-9606 |
DOI-Link der Erstveröffentlichung: |
URN / URL: |
Zusammenfassung, Abstract
It is suggested that the main mechanism for neutral dissociation of the I, I′, and I′′ vibronic progressions in O2 is due to their interaction with the vibrational continuum of the 1π-1u(A2 Πu)3sσg 3Πu(vε) Rydberg state (J state) leading to the formation of the O(2p4 3P) + O*(2p3(4S)3s 3S) fragments. In order to justify this, the O I 2p3(4S)3s 3S → 2p4 3P fluorescence emission cross section following the neutral dissociation of the O2 1π-1u(a 4Πu)4sσg/3dδg/3dσg 3Πu(v) Rydberg states is simulated in the exciting-photon energy range of 14.636-16.105 eV. The results of high-resolution measurements (H. Liebel et al., J. Phys. B34, 2581 (2001)) can be reproduced if a small adjustment of the computed potential curve of the J state is applied. Non-Franck-Condon resonant intensity distributions of the I, I′, and I′′ progressions observed in the experiment are qualitatively explained by the presence of the O2 1π-1g(X 2Πg)npσu/nfσu/nfδu 3Πu perturber states. Present calculations allow to decide between two different assignments of the I, I′, and I′′ states available in literature.
It is suggested that the main mechanism for neutral dissociation of the I, I′, and I′′ vibronic progressions in O2 is due to their interaction with the vibrational continuum of the 1π-1u(A2 Πu)3sσg 3Πu(vε) Rydberg state (J state) leading to the formation of the O(2p4 3P) + O*(2p3(4S)3s 3S) fragments. In order to justify this, the O I 2p3(4S)3s 3S → 2p4 3P fluorescence emission cross section following the neutral dissociation of the O2 1π-1u(a 4Πu)4sσg/3dδg/3dσg 3Πu(v) Rydberg states is simulated in the exciting-photon energy range of 14.636-16.105 eV. The results of high-resolution measurements (H. Liebel et al., J. Phys. B34, 2581 (2001)) can be reproduced if a small adjustment of the computed potential curve of the J state is applied. Non-Franck-Condon resonant intensity distributions of the I, I′, and I′′ progressions observed in the experiment are qualitatively explained by the presence of the O2 1π-1g(X 2Πg)npσu/nfσu/nfδu 3Πu perturber states. Present calculations allow to decide between two different assignments of the I, I′, and I′′ states available in literature.
