Correction: Real-time structural dynamics of the ultrafast solvation process around photo-excited aqueous halides.

[This corrects the article DOI: 10.1039/D4SC01912A.].

Real-time structural dynamics of the ultrafast solvation process around photo-excited aqueous halides.

This work investigates and describes the structural dynamics taking place following charge-transfer-to-solvent photo-abstraction of electrons from I and Br ions in aqueous solution following single- and 2-photon excitation at 202 nm and 400 nm, respectively. A Time-Resolved X-ray Solution Scattering (TR-XSS) approach with direct sensitivity to the structure of the surrounding solvent as the water molecules adopt a new equilibrium configuration following the electron-abstraction process is utilized to investigate the structural dynamics of solvent shell expansion and restructuring in real-time. The structural sensitivity of the scattering data enables a quantitative evaluation of competing models for the interaction between the nascent neutral species and surrounding water molecules.

Eliminating finite-size effects on the calculation of x-ray scattering from molecular dynamics simulations.

Structural studies using x-ray scattering methods for investigating molecules in solution are shifting focus toward describing the role and effects of the surrounding solvent. However, forward models based on molecular dynamics (MD) simulations to simulate structure factors and x-ray scattering from interatomic distributions such as radial distribution functions (RDFs) face limitations imposed by simulations, particularly at low values of the scattering vector q. In this work, we show how the value of the structure factor at q = 0 calculated from RDFs sampled from finite MD simulations is effectively dependent on the size of the simulation cell.

Exploring fingerprints of ultrafast structural dynamics in molecular solutions with an X-ray laser.

We apply ultrashort X-ray laser pulses to track optically excited structural dynamics of [Ir(dimen)] molecules in solution. In our exploratory study we determine angular correlations in the scattered X-rays, which comprise a complex fingerprint of the ultrafast dynamics. Model-assisted analysis of the experimental correlation data allows us to elucidate various aspects of the photoinduced changes in the excited molecular ensembles.