Prospects of Using High-Intensity THz Pulses To Induce Ultrafast Temperature-Jumps in Liquid Water.

Ultrashort, high-intensity terahertz (THz) pulses, e.g., generated at free-electron laser facilities, allow for direct investigation as well as the driving of intermolecular modes in liquids like water and thus will deepen our understanding of the hydrogen bonding network. In this work, the temperature-jump (T-jump) of water induced by THz radiation is simulated for ten different THz frequencies in the range from 3 to 30 THz and five different pulse intensities in the range from 1 × 1011 to 5 × 1012 W/cm2 employing both ab initio molecular dynamics (AIMD) and force field molecular dynamics (FFMD) approaches. The most efficient T-jump can be achieved with 16 THz pulses. Three distinct T-jump mechanisms can be uncovered. For all cases, the T-jump mechanism proceeds within tens of femtoseconds (fs). For frequencies between 10 and 25 THz, most of the energy is initially transferred to the rotational degrees of freedom. Subsequently, the energy is redistributed to the translational and intramolecular vibrational degrees of freedom within a maximum of 500 fs. For the lowest frequencies considered (7 THz and below), translational and rotational degrees of freedom are heated within tens of fs as the THz pulse also couples to the intermolecular vibrations. Subsequently, the intramolecular vibrational modes are heated within a few hundred fs. At the highest frequencies considered (25 THz and above), vibrational and rotational degrees of freedom are heated within tens of fs, and energy redistribution to the translational degrees of freedom happens within several hundred fs. Both AIMD and FFMD simulations show a similar dependence of the T-jump on the frequency employed. However, the FFMD simulations overestimate the total energy transfer around the main peak and drop off too fast toward frequencies higher and lower than the main peak. These differences can be rationalized by missing elements, such as the polarizability, in the TIP4P/2005f force field employed. The feasibility of performing experiments at the studied frequencies and intensities as well as important issues such as energy efficiency, penetration depth, and focusing are discussed.