Partial and Contingent Recoil-Frame Covariance-Map Imaging.

Abstract

When applied to multimass velocity-map imaging data, covariance analysis reveals correlations between different fragment ions formed from the same parent molecule and can provide detailed insights into the fragmentation dynamics. Covariances between the time-of-flight signals for two different ions show that they are formed in the same event, while covariances between their velocity-map images, often referred to as "recoil-frame covariances", reveal details of the correlated motion of the two fragments. In many cases, covariance analysis is complicated by the fact that fluctuations in experimental parameters such as laser or molecular beam intensities can lead to apparent correlations between unrelated ions. In the context of time-of-flight covariance signals, this problem has been overcome by the introduction of partial covariance and contingent covariance approaches. Here, we apply these approaches to recoil-frame covariance-map images. We also demonstrate that in many cases the total signal within each experimental cycle can be used as a useful proxy for independent explicit measurements of the varying experimental parameter(s).