Three-dimensional modeling of EXAFS spectral mixtures by combining Monte Carlo Simulations and Target Transformation Factor Analysis

We developed a new method for the three-dimensional modeling of Extended X-ray Absorption Fine Structure (EXAFS) spectra, which is suited to extract the local structure of aqueous metal complexes from spectral mixtures of several components. The new method combines two techniques: Monte Carlo simulation and Target Transformation Factor Analysis (TFA). Monte Carlo simulation is used to create random arrangements between the X-ray absorbing metal ion and the ligand atoms, and to calculate the theoretical EXAFS spectrum of each arrangement. The theoretical EXAFS spectrum is then introduced as test spectrum in the TFA procedure, in order to test whether the test spectrum is likely a component of the spectral mixtures or not. This coupled procedure is repeated, until the error in the test spectrum is minimized. The new method is thus able to isolate and refine the structure of complexes from spectral mixtures and to determine their relative concentrations, based solely on an estimate of the ligand structure. The performance of the proposed method was validated using uranium LIII-edge EXAFS spectra of binary mixtures of two uranium(VI) 3,4-dihydoxy benzoic acid complexes.