Clarification of the electronic asymmetry of Lgr; doublets in3Pgr; electronic states of diatomic molecules

摘要

The reflection symmetry of the spatial part of the electronic wave function for3Pgr; diatomic molecular states is examined carefully for the individual Lgr; doublet levels by means of an approach presented earlier lsqb;M. H. Alexander and P. J. Dagdigian, J. Chem. Phys.80, 4325 (1984)rsqb;. The results are: For a3Pgr; molecule in Hundrsquo;s case (a) the electronic wave function in the OHgr;=1 (F2)elevels will be antisymmetric and, in the theflevels, symmetric with respect to reflection of the spatial coordinates of the electrons in the plane of rotation of the molecule. The electronic wave functions in theF1andF3levels will not have a defined plane of symmetry. By contrast, in the Hundrsquo;s case (b) highJlimit, the electronic wave function in theF1e,F2thinsp;f, andF3elevels will be antisymmetric and, in theF1thinsp;f,F2e, andF3thinsp;flevels, symmetric with respect to reflection. Thus, the symmetry of the wave functions in theF2Lgr;hyphen;doublet levels reverses with the passage from case (a) to case (b). In the case (b) limit, the main branchPandRlines of a3Pgr;ndash;3Sgr;minus;transition will probe antisymmetric levels, irrespective of theFilevel of the3Pgr; state, while the main branchQlines will probe symmetric levels. This will be reversed for a3Pgr;ndash;3Sgr;+transition. At lowJ, in the case (a) limit, in a3Pgr;ndash;3Sgr;minus;transition theP2iandR2ilines withiodd and theQ2ilines withieven will probe antisymmetric levels, while theP2iandR2ilines withieven and theQ2ilines withiodd will probe symmetric levels; the other 18 rotational branches probe levels with no wellhyphen;defined reflection symmetry.