Communication: HK propagator uniformized along a one-dimensional manifold in weakly anharmonic systems.
A simplification of the Heller-Herman-Kluk-Kay (HK) propagator is presented that does not suffer from the need for an increasing number of trajectories with dimensions of the system under study. This is accomplished by replacing HK's uniformizing integral over all of phase space by a one-dimensional curve that is appropriately selected to lie along the fastest growing manifold of a defining trajectory. It is shown that this modification leads to eigenspectra of quantum states in weakly anharmonic systems that can outperform the comparatively computationally cheap thawed Gaussian approximation method and frequently approach the accuracy of spectra obtained with the full HK propagator.
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
Lucas
L
Kocia
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
Eric J
EJ
Heller