Verification labels for rovibronic quantum-state energy uncertainties

Abstract

Abstract Transition wavenumbers contained in line-by-line rovibronic databases can be compromised by errors of various nature. When left undetected, these errors may result in incorrect quantum-state energies, potentially compromising a large number of derived spectroscopic data. Spectroscopic networks treat the complete set of line-by-line spectroscopic data as a large graph, and through a least-squares refinement the measured line positions are converted into empirical quantum-state energies. Spectroscopic networks also offer a highly useful framework to develop mathematical tools helping to identify possible errors and conflicts within the dataset. For example, wavenumber errors can be detected by checking for violations of the law of energy conservation. This paper describes a new graph-theory tool, which results in so-called verification labels for the quantum states. Verification labels help to express the vulnerability of a calculated empirical energy value and its uncertainty against possible wavenumber errors, providing complementary information to simple statistical uncertainties.