Charge-overlap cluster calculations [Wheatley, R. J. Chem. Phys. Lett. 1998, 294, 487], in which the electronic structure of a central ion is modified self-consistently by the frozen densities of its neighbors, are used to model induced dipoles in the condensed-phase alkali metal halides. Two distinct effects of overlap are identified: exchange-repulsion and Coulomb corrections. For anions, both substantially reduce the dipole from its asymptotic value; for cations, the two short-range effects are opposed, producing small net short-range corrections of different sign for different alkali metal cations.
- IONIC SYSTEMS, AB-INITIO, QUADRUPOLE POLARIZATION, INTERIONIC INTERACTIONS, DIPOLE POLARIZABILITY, CRYSTAL-STRUCTURE, OVERLAP MODEL, FLUORIDE-ION, ALKALI, DYNAMICS
Domene Nunez, C., Fowler, P. W., Madden, P. A., Xu, J., Wheatley, R. J., & Wilson, M. (2001). Short-range contributions to the polarization of cations. The Journal of Physical Chemistry A, 105(16), 4136-4142. https://doi.org/10.1021/jp004173m