Reconciling Semiclassical and Bohmian Mechanics: IV. Multisurface Dynamics

TL;DR

This paper extends a bipolar wave decomposition method to multisurface quantum dynamics, linking semiclassical and Bohmian mechanics, and demonstrates its effectiveness on benchmark scattering problems.

Contribution

It generalizes the bipolar wave decomposition approach for multisurface systems, connecting intersurface and bipolar transitions, and applies it to complex scattering scenarios.

Findings

The method accurately models multisurface scattering dynamics.

Bipolar trajectories remain well-behaved with complex wavefunctions.

The approach provides insights into intersurface transition mechanisms.

Abstract

In previous articles [J. Chem. Phys. 121 4501 (2004), J. Chem. Phys. 124 034115 (2006), J. Chem. Phys. 124 034116 (2006)] a bipolar counter-propagating wave decomposition, Psi = Psi+ + Psi-, was presented for stationary states Psi of the one-dimensional Schrodinger equation, such that the components Psi+- approach their semiclassical WKB analogs in the large action limit. The corresponding bipolar quantum trajectories are classical-like and well-behaved, even when Psi has many nodes, or is wildly oscillatory. In this paper, the method is generalized for multisurface scattering applications, and applied to several benchmark problems. A natural connection is established between intersurface transitions and (+/-) transitions.