Time-resolved terahertz-Raman spectroscopy reveals that cations and anions distinctly modify intermolecular interactions of water

The solvation of ions changes the physical, chemical and thermodynamic properties of water, and the microscopic origin of this behaviour is believed to be ion-induced perturbation of water's hydrogen-bonding network. Here we provide microscopic insights into this process by monitoring the dissipation of energy in salt solutions using time-resolved terahertz-Raman spectroscopy. We resonantly drive the low-frequency rotational dynamics of water molecules using intense terahertz pulses and probe the Raman response of their intermolecular translational motions. We find that the intermolecular rotational-to-translational energy transfer is enhanced by highly charged cations and is drastically reduced by highly charged anions, scaling with the ion surface charge density and ion concentration. Our molecular dynamics simulations reveal that the water-water hydrogen-bond strength between the first and second solvation shells of cations increases, while it decreases around anions. The opposite effects of cations and anions on the intermolecular interactions of water resemble the effects of ions on the stabilization and denaturation of proteins.

Automated summary

The solvation of ions alters the properties of water, and the underlying mechanism is believed to be the disruption of water's hydrogen-bonding network caused by ions. This study investigates the dissipation of energy in salt solutions and reveals that highly charged cations enhance the rotational-to-translational energy transfer, while highly charged anions reduce it. Molecular dynamics simulations provide insights into the changes in the hydrogen-bond strength between water molecules induced by cations and anions.