## Abstract

The van der Waals (dispersion) interaction between an atom and a cluster or between two clusters at large separation is calculated by considering each cluster as a point particle, characterized by a polarizability tensor. For the extreme limit of very large separation, the fully retarded regime, one needs to know just the static polarizability in order to determine the interaction. This polarizability is evaluated by including all many-body (MB) intracluster atomic interactions self-consistently. The results of these calculations are compared with those obtained from various alternative methods. One is to consider each cluster as a collection of many atoms and evaluate the sum of two-body interatomic interactions, a common assumption. An alternative method is to include three-body atomic interactions as a MB correction term in the total energy. A comparison of these results reveals that the contribution of the higher-than-three-body MB interactions is always attractive and non-negligible even at such a large separation, in contrast to common assumptions. The procedure employed is quite general and is applicable, in principle, to any shape or size of dielectric cluster. We present numerical results for clusters composed of atoms with polarizability consistent with silica, for which the higher-than-three-body MB correction term can be as high as 42% of the atomic pairwise sum. This result is quite sensitive to the anisotropy and orientation of the cluster, in contrast to the result found in the additive case. We also present a power law expansion of the total van der Waals interaction as a series of n -body interaction terms.

Original language | English (US) |
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Article number | 174303 |

Journal | Journal of Chemical Physics |

Volume | 125 |

Issue number | 17 |

DOIs | |

State | Published - 2006 |

## All Science Journal Classification (ASJC) codes

- Physics and Astronomy(all)
- Physical and Theoretical Chemistry