Using Activation Energies to Elucidate Mechanisms of Water Dynamics

Zeke A Piskulich (1) , Damien Laage (2) , Ward H Thompson (1)

1 KU - University of Kansas [Lawrence]
2 PASTEUR - Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640)

Recent advances in the calculation of activation energies are shedding new light on the dynamical timescales of liquid water. In this Perspective, we examine how activation energies elucidate the central, but not singular, role of the exchange of hydrogen-bond (H-bond) partners that rearranges the H-bond network of water. The contributions of other motions to dynamical timescales and their associated activation energies are discussed along with one case, vibrational spectral diffusion, where H-bond exchanges are not mechanistically significant. Nascent progress on outstanding challenges, including descriptions of non-Arrhenius effects and activation volumes, are detailed along with some directions for future investigations.

Domaines: Chimie théorique et/ou physique

Zeke A Piskulich, Damien Laage, Ward H Thompson. Using Activation Energies to Elucidate Mechanisms of Water Dynamics. Journal of Physical Chemistry A, 2021, 125 (46), pp.9941-9952. ⟨10.1021/acs.jpca.1c08020⟩. ⟨hal-03420260⟩