title: Semiclassical treatment of quantum propagation with nonlinear classical dynamics: A third-order thawed Gaussian approximation.
abstract: The time-dependent WKB approximation for a coherent state is expanded to third order around a guiding real trajectory, allowing for the novel treatment of nonlinearity in its semiclassical dynamics, which is generally present in all physical systems far from the classical regime. The result is a closed-form solution consisting of a linear combination of Airy functions and their derivatives multiplied by an exponential. The expression's ability to capture nonlinearity is demonstrated by examining the autocorrelation of initial coherent states in anharmonic systems with few to many contributing periodic orbits. Its accuracy is compared to the quadratic expansion and found to be superior in regimes of ℏ where the curvature begins to be significant, as expected. Moreover, the expression is shown to be a real-trajectory uniformization over two coalescing saddle points that are emblematic of significant curvature. This extends real-trajectory time-dependent wave-packet semiclassical methods to highly anharmonic systems for the first time and establishes their regime of validity.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Lucas
authors.initials: L
authors.lastname: Kocia
authors.affiliation: Department of Physics, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Anna
authors.initials: A
authors.lastname: Klales