Semiclassical demonstration of mode specificity in the tunneling splitting in a model of the malonaldehyde molecule
Abstract
A semiclassical model is used to calculate the tunneling splitting in a model of the malonaldehyde molecule to determine the extent to which mode-specific behavior might exist for malonaldehyde and other topologically similar systems. Ensembles of 2500 classical trajectories corresponding to various degrees of mode-selective excitation were computed on the model potential-energy surface by Hutchinson. Tunneling was incorporated by using a combination of the "classical-plus-tunneling" model of Waite and Miller and a newer variant by Makri and Miller. The results indicate a sensitive dependence of the splitting on the initial conditions. Extension of the method to full-dimensional calculations is discussed.
- Publication:
-
Chemical Physics Letters
- Pub Date:
- June 1992
- DOI:
- 10.1016/0009-2614(92)85642-N
- Bibcode:
- 1992CPL...193..347S