Structural relaxation, viscosity, and network connectivity in a hydrogen bonding liquid. Issue 38 (31st July 2017)

• Record Type: Journal Article
• Authors: Perticaroli, Stefania; Mostofian, Barmak; Ehlers, Georg; Neuefeind, Joerg C.; Diallo, Souleymane O.; Stanley, Christopher B.; Daemen, Luke; Egami, Takeshi; Katsaras, John; Cheng, Xiaolin; Nickels, Jonathan D.
• Is Part Of: Physical chemistry chemical physics. Volume 19:Issue 38(2017)
• Page Start: 25859
• Page End: 25869
• Publication Date: 2017-07-31
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c7cp04013j
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The structure and dynamics of the model H-bonding liquid, n -methylacetamide (NMA) have been studied, revealing the connection between the timescale of H-bond network reorganization and viscosity. Abstract : In liquids, the ability of neighboring molecules to rearrange and jostle past each other is directly related to viscosity, the property which describes the propensity to flow. The presence of hydrogen bonds (H-bonds) complicates the molecular scale picture of viscosity. H-Bonds are attractive, directional interactions between molecules which, in some cases, result in transient network structures. In this work, we use experimental and computational methods to demonstrate that the timescale of H-bond network reorganization is the dominant dynamical timescale associated with viscosity for the case of the model H-bonding liquid n -methylacetamide (NMA). This molecule is a peptide analog which forms a transient linear H-bond network. Individual H-bond lifetimes and dynamical fluctuations were observed on the timescale of 1.5 ps, while collective motions and the longest lived population of H-bond partner lifetimes were observed on the order of 20 ps, in agreement with the Maxwell relaxation time. This identifies a mechanism which may aid in understanding the emergence of various complex phenomena arising from transient molecular structures, with implications ranging from the internal dynamics of proteins, to the glass transition, to better understanding the origins of the unique properties of H-bonding liquids.