The negative ion states of HClminus;that go asymptotically to the Clminus;+H and Hminus;+Cl asymptotes have been studied as a function of the internuclear distance using firsthyphen;order configuration interaction wave functions. The 1thinsp;2Sgr;+, 2thinsp;2Sgr;+, and 1thinsp;2Pgr; states all cross the neutral HCl energy curve. To the right of the crossing all three curves are bound relative to their asymptotes and exhibit energy minima. The crossings occur on the left hand limbs of the negative ion curves. To the left of the crossing the lowest negative ion curve mimics the neutral and the attached electron is in an orbital which is as diffuse as the basis set permits. Several roots of the FOCI were examined in the unstable region. A root that has a large component of the rsquo;rsquo;tightrsquo;rsquo; wave function appears in a number of the calculations and possibly can be attributed to a broad resonance. Transition and dipole moments of the bound energy curves exhibit the behavior expected of charge transfer interaction and polarization among these states.
展开▼
