The rates of dissociation of several vibrational states of nπ* excited (C–1A′) DCN have been determined via quantum dynamical means in which only the CD stretching and DCN bending motions are treated. The ab initio configuration interaction potential energy surface used in our earlier classical trajectory study of these same dissociation rates was employed in the present study. The results of this quantal study tend to support our earlier prediction that v2→v1 (bending-to-stretching) energy transfer plays an important role in determining the dissociation rates of these vibronic states. Surprisingly, the absolute rates obtained via the quantum method are in quite close agreement with a certain component of the classically determined rates.
We have performed coordinate rotated configuration interaction calculations on well-studied Feshbach resonances of H-and He-and on *P shape resonances of Be-and Mg-. The focus of our efforts was the dependence of computed resonance energies on both the quality of the atomicorbital basis and the level of treatment of electron correlation. Our results indicate that great care must be taken to guarantee that a basis is adequate; commonly used quantum-chemistry bases are probably far from satisfactory. Our findings also indicate that a proper treatment of inner-shell orbitals within coordinate rotation calculations is a formidable task. We are therefore encouraged to look carefully for modified coordinate rotation techniques that focus on the active valence-level orbitals and may avoid spurious complex energies arising from improper treatment of inner shells. 2 ~~
The spectral quantization method which was successfully used previously to study bound state energies and wave functions of C 1A′DCN is extended to the low-lying metastable states of this same system. The potential energy surface employed involves the same ab initio calculational data as was used in our earlier classical trajectory and purely quantal studies. Energies and wave functions for the metastable states of DCN obtained by spectral quantization are compared to those achieved in the presumably accurate quantal study. The agreement between the quantal and spectal quantized wave function is not nearly as pleasing for these metastable states as it was for the bound states.
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