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.

Ultrafast energy transfer to liquid water by sub-picosecond high-intensity terahertz pulses: an ab initio molecular dynamics study.

Sub-picosecond heating of bulk water is accomplished by ultrashort and intense THz pulses which are able to transfer a large amount of energy to the liquid. The energy transferred corresponds to a temperature jump of about 600 K. Liquid water becomes a structureless and hot gas-like system still at the density of the liquid, in which the hydrogen-bonding structure has been washed out.

Molecular polarizability anisotropy of liquid water revealed by terahertz-induced transient orientation.

Reaction pathways of biochemical processes are influenced by the dissipative electrostatic interaction of the reagents with solvent water molecules. The simulation of these interactions requires a parametrization of the permanent and induced dipole moments. However, the underlying molecular polarizability of water and its dependence on ions are partially unknown. Here, we apply intense terahertz pulses to liquid water, whose oscillations match the timescale of orientational relaxation. Using a combination of terahertz pump / optical probe experiments, molecular dynamics simulations, and a Langevin dynamics model, we demonstrate a transient orientation of their dipole moments, not possible by optical excitation. The resulting birefringence reveals that the polarizability of water is lower along its dipole moment than the average value perpendicular to it. This anisotropy, also observed in heavy water and alcohols, increases with the concentration of sodium iodide dissolved in water. Our results enable a more accurate parametrization and a benchmarking of existing and future water models.

Subpicosecond energy transfer from a highly intense THz pulse to water: A computational study based on the TIP4P/2005 rigid-water-molecule model.

The dynamics of ultrafast energy transfer to water clusters and to bulk water by a highly intense, subcycle THz pulse of duration ≈150 fs is investigated in the context of force-field molecular dynamics simulations. We focus our attention on the mechanisms by which rotational and translational degrees of freedom of the water monomers gain energy from these subcycle pulses with an electric field amplitude of up to about 0.6 V/Å. It has been recently shown that pulses with these characteristics can be generated in the laboratory [C. Vicario, B. Monoszlai, and C. P. Hauri, Phys. Rev. Lett. 112, 213901 (2014)]. Through their permanent dipole moment, water molecules are acted upon by the electric field and forced off their preferred hydrogen-bond network conformation. This immediately sets them in motion with respect to one another as energy quickly transfers to their relative center of mass displacements. We find that, in the bulk, the operation of these mechanisms is strongly dependent on the initial temperature and density of the system. In low density systems, the equilibration between rotational and translational modes is slow due to the lack of collisions between monomers. As the initial density of the system approaches 1 g/cm(3), equilibration between rotational and translational modes after the pulse becomes more efficient. In turn, low temperatures hinder the direct energy transfer from the pulse to rotational motion owing to the resulting stiffness of the hydrogen bond network. For small clusters of just a few water molecules we find that fragmentation due to the interaction with the pulse is faster than equilibration between rotations and translations, meaning that the latter remain colder than the former after the pulse. In contrast, clusters with more than a few tens of water molecules already display energy gain dynamics similar to water in condensed phases owing to inertial confinement of the internal water molecules by the outer shells. In these cases, a complete equilibration becomes possible.

Ultrafast Energy Transfer from Solvent to Solute Induced by Subpicosecond Highly Intense THz Pulses.

The ultrafast energy transfer from an intense, subpicosecond THz pulse to bulk water at 300 K and density 1 g/cm(3) is simulated by ab initio molecular dynamics with explicit inclusion of the laser pulse. A 200 fs subcycle pulse of intensity 5 × 10(12) W/cm(2) corresponding to a peak field amplitude of 0.6 V/Å and achievable nowadays using optical rectification techniques results in a temperature jump from 300 K up to ∼1000 K within the first picosecond after the pulse. We discuss in detail the time-dependent structural changes caused by the THz pulse in the water medium and suggest possible ways to measure those changes by pump-probe experimental techniques. The ultrafast energy transfer from the energized water molecules to a solute molecule is studied on a test system, phenol. We find that phenol is, in the gas phase, insensitive to the THz pulse and only gains energy in solution via collisional energy transfer with the water molecules in its environment. The reason for this is found in the mode of interaction of the THz pulse with the aqueous medium. In short, water molecules respond mainly through their permanent dipole moments trying to orient themselves in the strong electric field of the pulse and disrupting their hydrogen-bonding structure. As compared with the water molecule, phenol has a smaller but still substantial permanent dipole moment. The moments of inertia of phenol are, however, too large for it to rotate in the short duration of the THz pulse. Therefore, the direct heating-up mechanism is mostly selective to the solvent molecules, whereas the solute heats up indirectly via collisions with its hot environment in about 1 to 2 ps.