Sub-picosecond energy transfer from a highly intense THz pulse to water: a computational study based on the TIP4P/2005 model

TL;DR

This computational study investigates how a highly intense, sub-cycle THz pulse rapidly transfers energy to water molecules, affecting their rotational and translational motions depending on temperature and density, with implications for ultrafast water dynamics.

Contribution

The paper provides new insights into the mechanisms of ultrafast energy transfer from intense THz pulses to water, highlighting the roles of initial conditions and molecular interactions.

Findings

Energy transfer efficiency depends on initial temperature and density.

Low density systems exhibit slow rotational-translational equilibration.

Small water clusters fragment faster than they equilibrate after pulse interaction.

Abstract

The dynamics of ultrafast energy transfer to water clusters and to bulk water by a highly intense, sub-cycle THz pulse of duration $\approx$~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 sub-cycle pulses with an electric field amplitude of up to about 0.6~V/{\AA}. It has been recently shown that pulses with these characteristics can be generated in the laboratory [PRL 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.