Short-time dynamics through conical intersections in macrosystems. II. Applications.
We present several numerical applications based upon the effective-mode formulation for the short-time dynamics through conical intersections in macrosystems, as detailed in the preceding paper and first proposed by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)]. The macrosystem, containing a vast number of nuclear degrees of freedom (modes), is decomposed into a system part and an environment part. Only three effective environmental modes are needed-together with the system's modes-to accurately calculate the low resolution spectra and the short-time dynamics of the entire macrosystem. For the systems discussed here, results are compared to those of a full quantum wave-packet propagation. Some rules are extracted to provide general tendencies; these rules allow one to understand and predict the dynamical properties in more general situations where the exact quantum dynamics of the macrosystem is out of reach.
Gindensperger
Etienne
E
Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany. etienne@tc.pci.uni-heidelberg.de
Burghardt
Irene
I
Cederbaum
Lorenz S
LS