On the accuracy of the chemically significant eigenvalue method
Name
Holtorf_Green_2023_dspace_upload.pdf
Size
759.44 KB
Format
Adobe PDF
Checksum (MD5)
52fd3d322281e4b7e9d4158f74839083
Author(s)
Holtorf, Flemming
Green, William H.
Date Issued
October 9, 2023
Journal
Journal of Chemical Physics
Publisher
AIP Publishing
Citation
Holtorf, Flemming and Green, William H. 2023. "On the accuracy of the chemically significant eigenvalue method." Journal of Chemical Physics, 159 (14).
Version
Author's final manuscript
Abstract
We study the accuracy and convergence properties of the chemically significant eigenvalues method as proposed by Georgievskii et al. [J. Phys. Chem. A 117, 12146-12154 (2013)] and its close relative, dominant subspace truncation, for reduction of the energy-grained master equation. We formally derive the connection between both reduction techniques and provide hard error bounds for the accuracy of the latter which confirm the empirically excellent accuracy and convergence properties but also unveil practically relevant cases in which both methods are bound to fall short. We propose the use of balanced truncation as an effective alternative in these cases.
Subjects
Physical and Theoretical Chemistry
General Physics and Astronomy
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Computer Science and Artificial Intelligence Laboratory
Terms of Use
Creative Commons Attribution-Noncommercial-Share Alike
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1063/5.0158782
