Journal or Book Title
Journal of Chemical Physics
The stability with respect to spin‐forbidden radiationless decay of the previously reported [J. Chem. Phys. 88, 7248 (1988)] asymmetric dimer of NO, N–N–O–O (a‐N2O2) is considered. The spin‐allowed decay channel a‐N2O2(1 A’)→N2O(X 1Σ+)+O(1 D) is endoergic. However, the spin‐forbidden decay channel a‐N2O2(1 A’)→N2O(X 1Σ+)+O(3 P) is exoergic. Large scale multireference configuration interactionwave functions, approximately 300 000–1 400 000 configuration state functions, based on double zeta polarization and triplet zeta polarization bases are used to study this process. The minimum energy crossing of the ground singlet 1 A’ state and the lowest excited triplet 3 A‘ state was determined as was the interstate spin–orbit coupling. This electronic structure data was used in the context of a simple one‐dimensional model to show that a‐N2O2 is rapidly predissociated to N2O(X 1Σ+) and O(3 P).
Copyright 1993 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
American Institute of Physics
Nguyen, Kiet A.; Gordon, Mark S.; Montgomery, John A. Jr.; Michels, H. Harvey; and Harkony, David R., "Theoretical studies of spin‐forbidden radiationless decay in polyatomic systems. II. Radiationless decay of a‐N2O2" (1993). Chemistry Publications. 250.