Hierarchy of effective modes for the dynamics through conical intersections in macrosystems.
An extension of the effective-mode theory for the short-time dynamics through conical intersections in macrosystems [L. S. Cederbaum et al., Phys. Rev. Lett. 94, 113003 (2005)] is proposed. 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 modes are needed-together with the system's modes-to accurately calculate low resolution spectra and the short-time dynamics of the entire macrosystem. Here, the authors propose an iterative scheme to construct a hierarchy of additional triplets of effective modes. This naturally extends the effective-mode formulation. By taking into account more and more triplets, the dynamics are accurately predicted for longer and longer times, and more resolved spectra can be calculated. Numerical examples are presented, computed using various numbers of additional effective modes.
Gindensperger
Etienne
E
Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
Köppel
Horst
H
Cederbaum
Lorenz S
LS
D002627:Chemistry, Physical / Q000379:methods*; D008956:Models, Chemical; D015233:Models, Statistical; D008962:Models, Theoretical; D011789:Quantum Theory; D012107:Research Design; D013598:Systems Theory