Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 41, 2013
Previous Article Next Article

Unified approach to multipolar polarisation and charge transfer for ions: microhydrated Na+

Author affiliations

Abstract

Electrostatic effects play a large part in determining the properties of chemical systems. In addition, a treatment of the polarisation of the electron distribution is important for many systems, including solutions of monatomic ions. Typically employed methods for describing polarisable electrostatics use a number of approximations, including atom-centred point charges and polarisation methods that require iterative calculation on the fly. We present a method that treats charge transfer and polarisation on an equal footing. Atom-centred multipole moments describe the charge distribution of a chemical system. The variation of these multipole moments with the geometry of the surrounding atoms is captured by the machine learning method kriging. The interatomic electrostatic interaction can be computed using the resulting predicted multipole moments. This allows the treatment of both intra- and interatomic polarisation with the same method. The proposed method does not return explicit polarisabilities but instead, predicts the result of the polarisation process. An application of this new method to the sodium cation in a water environment is described. The performance of the method is assessed by comparison of its predictions of atomic multipole moments and atom–atom electrostatic interaction energies to exact results. The kriging models are able to predict the electrostatic interaction energy between the ion and all water atoms within 4 kJ mol−1 for any of the external test set Na+(H2O)6 configurations.

Graphical abstract: Unified approach to multipolar polarisation and charge transfer for ions: microhydrated Na+

Back to tab navigation

Supplementary files

Article information


Submitted
29 Jul 2013
Accepted
05 Sep 2013
First published
05 Sep 2013

Phys. Chem. Chem. Phys., 2013,15, 18249-18261
Article type
Paper

Unified approach to multipolar polarisation and charge transfer for ions: microhydrated Na+

M. J. L. Mills, G. I. Hawe, C. M. Handley and P. L. A. Popelier, Phys. Chem. Chem. Phys., 2013, 15, 18249
DOI: 10.1039/C3CP53204F

Social activity

Search articles by author

Spotlight

Advertisements