Impact of finite‐temperature and condensed‐phase effects on theoretical X‐ray absorption spectra of transition metal complexes

The impact of condensed‐phase and finite‐temperature effects on the theoretical X‐ray absorption spectra of transition metal complexes is assessed. The former are included in terms of the all‐electron Gaussian and augmented plane‐wave approach, whereas the latter are taken into account by extensive ensemble averaging along second‐generation Car–Parrinello ab initio molecular dynamics trajectories. We find that employing the periodic boundary conditions and including finite‐temperature effects systematically improves the agreement between our simulated X‐ray absorption spectra and experimental measurements. © 2018 Wiley Periodicals, Inc. Theoretical condensed‐phase X‐ray absorption spectra, as computed by the combined second‐generation Car–Parrinello molecular dynamics and all‐electron Gaussian and augmented plane‐wave approach, suggest that the usage of periodic boundary conditions and inclusion of finite‐temperature effects entails a systematic improvement within the X‐ray absorption fine structure range.