Charge transfer and polarisability in ionic liquids: a case study
File(s)CTPOL_manuscript_revised_nofields.pdf (1.76 MB)
Accepted version
Author(s)
Type
Journal Article
Abstract
The practical use of ionic liquids (ILs) is benefiting from a growing understanding of the underpinning structural and dynamic properties, facilitated through classical molecular dynamics (MD) simulations. The predictive and explanatory power of a classical MD simulation is inextricably linked to the underlying force field. A key aspect of the forcefield for ILs is the ability to recover charge based interactions. Our focus in this paper is on the description and recovery of charge transfer and polarisability effects, demonstrated through MD simulations of the widely used 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4C1im][NTf2] IL. We study the charge distributions generated by a range of ab initio methods, and present an interpolation method for determining atom-wise scaled partial charges. Two novel methods for determining the mean field (total) charge transfer from anion to cation are presented. The impact of using different charge models and different partial charge scaling (unscaled, uniformly scaled, atom-wise scaled) are compared to fully polarisable simulations. We study a range of Drude particle explicitly polarisable potentials and shed light on the performance of current approaches to counter known problems. It is demonstrated that small changes in the charge description and MD methodology can have a significant impact; biasing some properties, while leaving others unaffected within the structural and dynamic domains.
Date Issued
2022-01-17
Date Acceptance
2021-12-24
Citation
Physical Chemistry Chemical Physics, 2022, 24 (5), pp.3144-3162
ISSN
1463-9076
Publisher
Royal Society of Chemistry
Start Page
3144
End Page
3162
Journal / Book Title
Physical Chemistry Chemical Physics
Volume
24
Issue
5
Copyright Statement
© the Owner Societies 2022.
Identifier
https://pubs.rsc.org/en/content/articlelanding/2022/CP/D1CP04592J
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
MOLECULAR-DYNAMICS SIMULATIONS
FORCE-FIELD
ATOMIC CHARGES
ELECTROSTATIC POTENTIALS
ELECTRONIC-STRUCTURE
DRUDE OSCILLATORS
FUKUI FUNCTION
MONTE-CARLO
DENSITY
ANIONS
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Chemical Physics
Publication Status
Published
Date Publish Online
2022-01-17