TY - JOUR
T1 - The (X 2∏g) nsσg 1,3∏g Rydberg states of O2
T2 - Spectra, structures and interactions
AU - Morrill, J. S.
AU - Ginter, M. L.
AU - Lewis, B. R.
AU - Gibson, S. T.
PY - 1999/7/1
Y1 - 1999/7/1
N2 - The results of a critical reexamination of previous experimental observations of the (X2∏g) nsσg 1,3∏g Rydberg states of O2 are employed to optimize a coupled-channel Schrödinger-equation (CSE) model describing rovibronic interactions among a number of 1,3∏g Rydberg and valence states. The results of calculations using this CSE model are compared with the experimental energy-level and predissociation linewidth data base. As a result of the optimization process, relevant potential-energy curves and Rydberg-valence, Rydberg-Rydberg, and valence-valence interactions are characterized for 1,3∏g states in the ∼6.5-9.5 eV region above the ground state of O2. The precision of these characterizations and the interpretation of the experimental observations are found to be limited by the quality of the existing data, which exhibit a number of inconsistencies that cannot be reconciled without new, well-characterized experimental studies. In spite of these difficulties, the present CSE model, as currently parametrized, represents a significant improvement over previous work, enabling identification of a number of previously unassigned spectral features associated with perturbation of the 3sσg d 1∏g state by the ∥ 1∏g valence state and an anomalous J sensitivity in predissociation branching ratios for the d(v = 1) level. In addition, the electronic structure and predissociation of the nsσg states for n≥4 are found to be strongly influenced by nsσg -(n-1)dσg Rydberg-Rydberg interactions.
AB - The results of a critical reexamination of previous experimental observations of the (X2∏g) nsσg 1,3∏g Rydberg states of O2 are employed to optimize a coupled-channel Schrödinger-equation (CSE) model describing rovibronic interactions among a number of 1,3∏g Rydberg and valence states. The results of calculations using this CSE model are compared with the experimental energy-level and predissociation linewidth data base. As a result of the optimization process, relevant potential-energy curves and Rydberg-valence, Rydberg-Rydberg, and valence-valence interactions are characterized for 1,3∏g states in the ∼6.5-9.5 eV region above the ground state of O2. The precision of these characterizations and the interpretation of the experimental observations are found to be limited by the quality of the existing data, which exhibit a number of inconsistencies that cannot be reconciled without new, well-characterized experimental studies. In spite of these difficulties, the present CSE model, as currently parametrized, represents a significant improvement over previous work, enabling identification of a number of previously unassigned spectral features associated with perturbation of the 3sσg d 1∏g state by the ∥ 1∏g valence state and an anomalous J sensitivity in predissociation branching ratios for the d(v = 1) level. In addition, the electronic structure and predissociation of the nsσg states for n≥4 are found to be strongly influenced by nsσg -(n-1)dσg Rydberg-Rydberg interactions.
UR - http://www.scopus.com/inward/record.url?scp=0000443080&partnerID=8YFLogxK
U2 - 10.1063/1.479264
DO - 10.1063/1.479264
M3 - Article
SN - 0021-9606
VL - 111
SP - 173
EP - 185
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 1
ER -