Solving the Trivial Crossing Problem While Preserving the Nodal Symmetry of the Wave Function
Name
acs.jctc.9b00302.pdf
Description
Published version
Size
1.78 MB
Format
Adobe PDF
Checksum (MD5)
0bdc829bd29f895f8d4cf34f9edd39a9
Author(s)
Lee, Elizabeth M. Y.
Willard, Adam P.
Date Issued
July 2019
Journal
Journal of Chemical Theory and Computation
Publisher
American Chemical Society (ACS)
Citation
Lee, Elizabeth M. Y. Lee and Willard, Adam P. "Solving the Trivial Crossing Problem While Preserving the Nodal Symmetry of the Wave Function." Journal of Chemical Theory and Computation 15, 8 (July 2019): 4332-4343 © 2019 American Chemical Society.
Version
Final published version
Abstract
In an adiabatic mixed quantum-classical simulation, the avoided crossing of weakly coupled eigenstates can lead to unphysical discontinuities in wave function dynamics, otherwise known as the trivial crossing problem. A standard solution to the trivial crossing problem eliminates spatial discontinuities in wave function dynamics by imposing changes to the eigenstate of the wave function. In this paper, we show that this solution has the side effect of introducing transient discontinuities in the nodal symmetry of the wave function. We present an alternative solution to the trivial crossing problem that preserves both the spatial and nodal structure of the adiabatic wave function. By considering a model of exciton dynamics on conjugated polymer systems, we show that failure to preserve wave function symmetry yields exciton dynamics that depends unphysically on polymer system size. We demonstrate that our symmetry-preserving solution to the trivial crossing problem yields more realistic dynamics and can thus improve the accuracy of simulations of larger systems that are prone to the trivial crossing problem. Keywords: Excitons; Monomers; Hamiltonians; Coupling reactions; Wave function
Subjects
Physical and Theoretical Chemistry
Computer Science Applications
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivs License
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/acs.jctc.9b00302
