Activation energies and the extended jump model: How temperature affects reorientation and hydrogen-bond exchange dynamics in water

• Published in: The Journal of chemical physics 2020-08, Vol.153 (7), p.074110-074110
• Main Authors: Piskulich, Zeke A., Laage, Damien, Thompson, Ward H.
• Format: Article
• Language: English
• Subjects: Activation energy; Aqueous solutions; Chemical bonds; Chemical Sciences; Computer simulation; Exchanging; Fluctuation theory; Hydrogen; Molecular interactions; or physical chemistry; Physics; Temperature dependence; Theoretical and
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0020015

Hydrogen-bond exchanges drive many dynamical processes in water and aqueous solutions. The extended jump model (EJM) provides a quantitative description of OH reorientation in water based on contributions from hydrogen-bond exchanges, or jumps, and the “frame” reorientation of intact hydrogen-bond pairs. Here, we show that the activation energies of OH reorientation in bulk water can be calculated accurately from the EJM and that the model provides a consistent picture of hydrogen-bond exchanges based on molecular interactions. Specifically, we use the recently developed fluctuation theory for dynamics to calculate activation energies, from simulations at a single temperature, of the hydrogen-bond jumps and the frame reorientation, including their decompositions into contributions from different interactions. These are shown to be in accord, when interpreted using the EJM, with the corresponding activation energies obtained directly for OH reorientation. Thus, the present results demonstrate that the EJM can be used to describe the temperature dependence of reorientational dynamics and the underlying mechanistic details.