Decoding Transient X-ray Absorption Spectra of Acetylacetone With Multireference Algebraic Diagrammatic Construction Theory

Abstract

Time-resolved X-ray absorption spectroscopy (TR-XAS) offers an element- and site-specific probe of coupled electronic and nuclear dynamics, but its interpretation requires methods that can treat multiconfigurational excited states across nonequilibrium nuclear ensembles. Here, we report time-resolved simulations of the acetylacetone (AcAc) transient X-ray absorption spectra by combining surface-hopping dynamics from complete active space second-order perturbation theory with multireference algebraic diagrammatic construction (MR-ADC). The simulated 20-200 fs spectra show a good agreement with experimental measurements and reveal that the TR-XAS response is governed by continuously evolving distributions of molecular geometries on the singlet potential energy surfaces (S2 and S1). In particular, absorption at 279.5-281.5 eV is enhanced for transient, nearly symmetric proton-sharing configurations, whereas the 284-286 eV profile reflects geometry-dependent C1s excitations modulated by proton transfer, bond alternation, and ring opening. For the long-time T_1 spectrum (7-10 ps), the principal features near 281.4 and 283.8 eV are assigned to central C 1s excitations into low-lying triplet pi-orbitals. Together, our simulations provide a more complete mechanistic picture of AcAc photorelaxation by directly linking ultrafast carbon K-edge signals to proton transfer, skeletal reorganization, internal conversion, and triplet formation.