On the accuracy of the chemically significant eigenvalue method.

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.