Journal of Chemical Sciences

, Volume 129, Issue 7, pp 883–890 | Cite as

A model with charges and polarizability for CS2 in an ionic liquid

  • RUTH M LYNDEN-BELLEmail author
Regular Article


The environment of a solute molecule in an ionic liquid is likely to have large fluctuating electrostatic fields, and so the electrostatic properties of such a solute including its charge distribution and its polarizability may make a difference to both its static and dynamic properties. We have developed a new model for the static electrostatic distribution in the CS2 molecule with 7 charged sites and anisotropic polarizability on the carbon site and isotropic polarizability on the sulfurs. We have investigated static and dynamic properties of the neat liquid and solutions of CS2 in an ionic liquid, [dmim][NTf2].

Graphical Abstract

Left: ab initio electrostatic potential (volt) on the vdW×1.5 surface of CS2; middle: difference between 3-site model and an initio; right: difference between 7-site model and ab inito.


CS2 electrostatic model site polarizability model ionic liquid solutions. 



This paper is dedicated to the memory of Charusita Chakravarty, a talented Theoretical Chemist and fine role model.


  1. 1.
    Tildesley D and Madden P 1981 An effective pair potential for liquid carbon disulfide Mol. Phys. 42 1137CrossRefGoogle Scholar
  2. 2.
    Torii H 2003 The role of atomic quadrupoles in intermolecular electrostatic interactions of polar and nonpolar molecules J. Chem. Phys. 119 2192CrossRefGoogle Scholar
  3. 3.
    Madden P and Tildesley D 1985 Interaction-induced contributions to Rayleigh and Rayleigh Scattering: a simulation study of CS2 Mol. Phys. 55 969CrossRefGoogle Scholar
  4. 4.
    Xue L, Tamas G, Gurung E and Quitevis E L 2014 Probing the Iinterplay between electrostatic and dispersion interactions in the solvation of nonpolar nonaromatic solute molecules in ionic liquids: An OKE spectroscopic sStudy of CS2/[Cn C 1im][NTf2] mixtures (n = 1-4) J. Chem. Phys. 140 164512CrossRefGoogle Scholar
  5. 5.
    Williams G J and Stone A J 2003 Distributed dispersion: a new approach J. Chem. Phys. 119 4620CrossRefGoogle Scholar
  6. 6.
    Misquitta A J, Stone A J and Price S L 2008 Accurate Induction Energies for Small Organic Molecules. 2. Development and Testing of Distributed Polarizability Models against SAPT(DFT) Energies J. Chem. Theory Comput. 4 19CrossRefGoogle Scholar
  7. 7.
    Misquitta A J and Stone A J 2016 Ab initio atom–atom potentials using CamCASP: Theory and application to many-body models for the pyridine dimer J. Chem. Theory Comput. 12 4184CrossRefGoogle Scholar
  8. 8.
    Adamo C and Barone V 1999 Toward reliable density functional methods without adjustable parameters: The PBE0 model J. Chem. Phys. 110 6158CrossRefGoogle Scholar
  9. 9.
    Tozer D J and Handy N C 1998 Improving virtual Kohn–Sham orbitals and eigenvalues: Application to excitation energies and static polarizabilities J. Chem. Phys. 109 10180CrossRefGoogle Scholar
  10. 10.
    Kendall R A, Dunning Thom H. and Harrison R J 1992 Electron affinities of the first-row atoms revisited. Systematic basis sets and wave functions J. Chem. Phys. 96 6796CrossRefGoogle Scholar
  11. 11.
    Lillestolen T C and Wheatley R 2008 Redefining the atom: atomic charge densities produced by an iterative stockholder approach Chem. Comm. 2008 5909CrossRefGoogle Scholar
  12. 12.
    Lillestolen T C and Wheatley R 2009 Atomic charge densities generated using an iterative stockholder approach J. Chem. Phys. 131 (144101)Google Scholar
  13. 13.
    Misquitta A J, Stone A J and Fazeli F 2014 Distributed Multipoles from a Robust Basis-Space Implementation of the Iterated Stockholder Atoms Procedure J. Chem. Theory Comput. 10 5405CrossRefGoogle Scholar
  14. 14.
    Stone A J 2013 In The theory of intermolecular forces 2nd edn. (Oxford: Oxford University Press) ISBN 978-0-19-967239-4CrossRefGoogle Scholar
  15. 15.
    Winn P J, Ferenczy G G and Reynolds C A 1997 Toward improved force fields. 1. Multipole-derived atomic charges J. Phys. Chem. A 101 5437CrossRefGoogle Scholar
  16. 16.
    Ferenczy G G, Winn P J and Reynolds C A 1997 Toward improved force fields. 2. Effective distributed multipoles J. Phys. Chem. A 101 5446CrossRefGoogle Scholar
  17. 17.
    Lillestolen T C and Wheatley R J 2007 First-Principles Calculation of Local Atomic Polarizabilities J. Phys. Chem. A 111 11141CrossRefGoogle Scholar
  18. 18.
    Gray C G and Gubbins K E 1984 In Theory of molecular fluids vol. 1: Fundamentals (Oxford: Oxford University Press)Google Scholar
  19. 19.
    Smith W, Forester T and Todorov I 2012 The DL_POLY classic user manual (STFC Daresbury Laboratory)Google Scholar
  20. 20.
    Lynden-Bell R M and Quitevis E L 2016 The importance of polarizability: Comparison of models of carbon disulphide in the ionic liquids [C1 C 1im][NTf2] and [C4 C 1im][NTf2] Phys. Chem. Chem. Phys. 18 16535CrossRefGoogle Scholar
  21. 21.
    Canongia Lopes J and Pádua A 2012 CL&P: A generic and systematic force field for ionic liquids modeling Theoretical Chemistry Accounts 131 1129CrossRefGoogle Scholar
  22. 22.
    Ködderman T, Paschek D and Ludwig R 2007 Molecular dynamic simulations of ionic liquids: A reliable description of structure, thermodynamics and dynamics Chem. Phys. Chem. 8 2464CrossRefGoogle Scholar
  23. 23.
    Allen M and Tildesley D 1991 Computer simulation of liquids 2nd ed. (New York: Oxford University Press)Google Scholar

Copyright information

© Indian Academy of Sciences 2017

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of CambridgeCambridgeU.K.

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