UNIMOLECULAR DISSOCIATION DYNAMICS OF HIGHLY VIBRATIONALLY EXCITED DCO((X)OVER-TILDE(2)A') .2. CALCULATION OF RESONANCE ENERGIES AND WIDTHSAND COMPARISON WITH HIGH-RESOLUTION SPECTROSCOPIC DATA

We present a theoretical study of the unimolecular dissociation of DCO in the electronic ground state, (X) over bar (1)A', using a new ab in itio potential energy surface. Altogether we have analyzed about 140 r esonances up to an energy of approximate to 1.4 eV above the D+CO thre shold, corresponding to the ninth overtone in the CO stretching mode ( v(2)=9) The agreement of the resonance positions and widths with recen t stimulated emission pumping measurements of Stock et al. [J. Chem. P hys. 106, 5333 (1997), the preceding article] is pleasing. The root-me an-square deviation from the experimental energies is only 16 cm(-1) o ver a range of about 16 500 cm(-1) and all trends of the resonance wid ths observed in the experiment are satisfactorily reproduced by the ca lculations. A strong 1:1:2 stretch-stretch-bend resonance prohibits a unique assignment for the majority of vibrational states. (C) 1997 Ame rican Institute of Physics.