Hydrogen bond lifetimes in supercritical methanol–water mixtures via MD simulation. (17th October 2016)

• Record Type: Journal Article
• Authors: Ono, Takumi; Ota, Masaki; Sato, Yoshiyuki; Inomata, Hiroshi
• Is Part Of: Molecular physics. Volume 114:Number 20(2016)
• Page Start: 2974
• Page End: 2982
• Publication Date: 2016-10-17
• Subjects: Molecular dynamics -- hydrogen bond lifetime -- supercritical state -- water–methanol mixture; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2016.1213435
• Languages: English
• ISSNs: 0026-8976

Abstract

ABSTRACT: Dynamical features of hydrogen bonds in methanol–water mixtures have been analysed in terms of lifetime in the wide range of conditions, including supercritical states, using a molecular dynamics simulation with flexible potential models. Hydrogen bond characteristics in methanol–water mixtures were investigated by considering the combination of molecular species and donor–acceptor of hydrogen-bonded molecules. The hydrogen bond lifetimes mainly depend on temperature, and those in supercritical condition were about 1/10th of that at ambient condition. Focusing on the composition dependence of the hydrogen bond lifetime, the unique behaviour of that resulting from hydration structure was observed. Moreover, the molecular combination, which showed the largest hydrogen bond lifetime, was different for ambient and high temperature and high pressure conditions. The relationship between hydrogen bond lifetime and molar volume was also calculated to discuss the hydrogen bond lifetime in terms of the collision frequency of molecules and the intermolecular distance. Abstract :