Polarisation of water under thermal fields: the effect of the molecular dipole and quadrupole moments.
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Published version
Author(s)
Chapman, Aidan
Bresme, Fernando
Type
Journal Article
Abstract
The investigation of the behaviour of water under thermal fields is important to understand thermoelectricity of solutions, aqueous suspensions, bioelectric effects or the properties of wet materials under spatially inhomogeneous temperature conditions. Here we discuss the response of bulk water to external thermal fields using non-equilibrium molecular dynamics simulations, and five widely used forcefields: TIP4P/2005, TIP4P/2005f, OPC, SPC/E and TIP3P. These models all show the thermal polarisation (TP) effect in bulk water, namely the build-up of an electrostatic field induced by the temperature gradient. The strength of this effect is ∼0.1-1 mV K-1 at near-standard conditions for all forcefields, supporting the generality of TP. Moreover, all the models predict a temperature inversion of the polarisation field, although the inversion temperatures vary significantly across different models. We rationalise this result by deriving theoretical equations that describe the temperature inversion as a balance of the isobaric thermal expansion, dipole orientation in the thermal field and the ratio of the molecular dipole/quadrupole moments. Lower ratios lead to higher inversion temperatures. Based on our results, we conclude that the accuracy of the forcefields describing the TP effect decreases as, TIP4P/2005 ∼ TIP4P/2005f ∼ OPC > SPC/E > TIP3P. At coexistence conditions, the inversion temperature is expected to be around 400 K. Furthermore, we establish a correlation between the TP inversion temperature and the temperature corresponding to the minimum of the liquid-vapour surface potential of water.
Date Issued
2022-05-30
Date Acceptance
2022-05-28
Citation
Physical Chemistry Chemical Physics, 2022, 24 (24), pp.14924-14936
ISSN
1463-9076
Publisher
Royal Society of Chemistry
Start Page
14924
End Page
14936
Journal / Book Title
Physical Chemistry Chemical Physics
Volume
24
Issue
24
Copyright Statement
© the Owner Societies 2022. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
License URL
Sponsor
The Leverhulme Trust
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/35678242
Grant Number
RPG-2018-384
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
LIQUID-VAPOR INTERFACE
ORIENTATIONAL STRUCTURE
SURFACE
ENHANCEMENT
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Publication Status
Published
Coverage Spatial
England
Date Publish Online
2022-05-30