On the connection between proton transport, structural diffusion, and reorientation of the hydrated hydroxide ion as a function of temperature

Publication year: 2011
Source: Chemical Physics Letters, In Press, Accepted Manuscript, Available online 13 June 2011

Zhonghua, Ma , Mark E., Tuckerman

The properties of the hydrated hydroxide ion OH- (aq) stand in sharp contrast to those of most other aqueous ions. Chief among these is its anomalously high mobility, which is shared only by the the aqueous hydronium ion H3O+ (aq). However, while the transport mechanism of H3O+ (aq) is now well understood, the details of OH- (aq) diffusion at ambient conditions are just beginning to emerge, and the effects of temperature on the transport mechanism remain largely unelucidated. Here, we undertake an ab initio molecular dynamics study of the effect of temperature on the solvation and transport of OH- (aq)….

Graphical abstract

 Graphical abstract:  Highlights: ►Temperature dependence of transport and reorientation of aqueous hydroxide. ► Analysis based on population correlation functions. ► Reorientation time increases at low temperature due to suppression of transport. ► High coordination solvation complexes dominate at low temperature.