Search for: All records

Theoretical simulations are critical to analyze and interpret the x-ray absorption spectrum of transient open-shell species. In this work, we propose a model of the many-body core-excited states of symmetric diradicals. We apply this model to analyze the carbon K-edge transitions of o-, m-, and p-benzyne, three organic diradicals with diverse and unusual electronic structures. The predictions of our model are compared with high-level multireference computations of the K-edge spectrum of the benzynes obtained with the driven similarity renormalization group truncated to third order. Our model shows the importance of a many-body treatment of the core-excited states of the benzynes and provides a theoretical framework to understand which properties of the ground state of these diradicals can be extracted from their x-ray spectrum. 

This work examines the accuracy and precision of x-ray absorption spectra computed with a multireference approach that combines generalized active space (GAS) references with the driven similarity renormalization group (DSRG). We employ the x-ray absorption benchmark of organic molecule (XABOOM) set, consisting of 116 transitions from mostly organic molecules [Fransson et al., J. Chem. Theory Comput. 17, 1618 (2021)]. Several approximations to a full-valence active space are examined and benchmarked. Absolute excitation energies and intensities computed with the GAS-DSRG truncated to second-order in perturbation theory are found to systematically underestimate experimental and reference theoretical values. Third-order perturbative corrections significantly improve the accuracy of GAS-DSRG absolute excitation energies, bringing the mean absolute deviation from experimental values down to 0.32 eV. The ozone molecule and glyoxylic acid are particularly challenging for second-order perturbation theory and are examined in detail to assess the importance of active space truncation and intruder states.