Alternative difference analysis scheme combining R-space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy

TL;DR

This paper introduces a new combined analysis scheme for time-resolved X-ray absorption spectroscopy that integrates R-space EXAFS difference fitting with a global optimization approach for XANES, enabling more accurate structural change detection.

Contribution

The novel scheme combines EXAFS difference fitting with a flexible, global optimization-based XANES fitting method for improved TR-XAS data analysis.

Findings

Reliable detection of distance change in Fe(phen)3 complex

Quantitative estimation of excitation population

Enhanced accuracy in structural change analysis

Abstract

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on laser-pump/X-ray probe method, is powerful in capturing the change of geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here we present a new analysis scheme for the TR-XAS difference fitting in both the Extended X-Ray Absorption Fine Structure (EXAFS) and the X-ray Absorption Near Edge Structure (XANES) region. R-space EXAFS difference fitting could quickly give main quantitative structure change of the first shell and provide reliable constraint on the range of the variables in XANES fit. XANES fitting part introduces global non-derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen)3 spin crossover complex and yielded the reliable distance change and the excitation population.