Interpretations of High-Order Transient Absorption Spectroscopies

Transient absorption (TA) spectroscopy has long been an invaluable tool for determining the energetics and dynamics of excited states in atomic, molecular, and solid-state systems. When pump pulse intensities are sufficiently high, the resulting TA spectra include both the generally desired third-order response of the studied material as well as responses that are higher order in the electric field amplitudes of the pulses. It has recently been shown that pump-intensity-dependent TA measurements allow separating the various orders of response of the TA signal, but the information content available in those higher orders has not been described. We give a general framework, intuition, and nomenclature for understanding the information contained in high-order TA spectra. Standard TA spectra are generally interpreted in terms of three fundamental processes: ground-state bleach (GSB), stimulated emission (SE), and excited state absorption (ESA), and we extend those concepts to higher order. Each order introduces two new processes: SE and ESA from highly excited states that were not accessible in lower orders. In addition, each order contain negations of lower-order processes, just as GSB is a negation of the linear absorption. We show the new spectral and dynamical information that is introduced at each order and show how the relative signs of the signals in different orders can be used to identify which processes are dominant.