Transformation of Time-Resolved Spectra to Lifetime-Resolved Spectra by Maximum Entropy Inversion of the Laplace Transform

Abstract

We present a method for the analysis of time-resolved spectroscopic data following first-order kinetics. The time traces at all the available spectroscopic channels (e.g., wavelength or wavenumber) are inverse Laplace transformed. The transformation is stabilized by the maximum entropy method generalized for solutions without sign-restriction. In this way, time-resolved spectra can be converted to lifetime-resolved spectra, where bands appear at coordinates corresponding to their spectroscopic maxima and time constant of appearance (negative amplitude) or disappearance (positive amplitude). From the lifetime-resolved spectra, the number of exponentially decaying components, their time constants, and their decay-associated spectra are readily available. Moreover, since bands are spread in two dimensions extra band-resolution is possible. We named this method of transforming time-resolved spectra into lifetime-resolved spectra multi-spectroscopic channel maximum entropy inversion of the Laplace transform (M-MaxEnt-iLT). The basis of M-MaxEnt-iLT is presented in detail and its properties and limitations are thoroughly discussed. We also show how the combination of M-MaxEnt-iLT with spectral smoothing or deconvolution can improve the appearance and/or band resolution of the obtained lifetime-resolved spectra.