Mesele Oluwaseun O, Vartia Anthony A, Laage Damien, Thompson Ward H
Department of Chemistry, University of Kansas , Lawrence, Kansas 66045, United States.
Department of Chemistry, Ecole Normale Supérieure, UMR ENS-CNRS-UPMC 8640 , 24 rue Lhmond, 75005 Paris, France.
J Phys Chem B. 2016 Mar 3;120(8):1546-59. doi: 10.1021/acs.jpcb.5b07692. Epub 2015 Sep 23.
Molecular dynamics simulations are used to investigate OH reorientation in the four isomeric butanols in their bulk liquid state to examine the influence of the arrangement of the steric bulk on the alcohol reorientational and hydrogen-bond (H-bond) dynamics. The results are interpreted within the extended jump model in which the OH reorientation is decomposed into contributions due to "jumps" between H-bond partners and "frame" reorientation of the intact H-bonded pair. Reorientation is fastest in iso-butanol and slowest in tert-butanol, while sec- and n-butanol have similar reorientation times. This latter result is a fortuitous cancellation between the jump and frame reorientation in the two alcohols. The extended jump model is shown to provide a quantitative description of the OH reorientation times. A detailed analysis of the jump times shows that a combination of entropic, enthalpic, and dynamical factors, including transition state recrossing effects, all play a role. A simple model based on the liquid structure is proposed to estimate the energetic and entropic contributions to the jump time. This represents the groundwork for a predictive model of OH reorientation in alcohols, but additional studies are required to better understand the frame reorientation and transition state recrossing effects.
