Many-body Dispersion Forces Research Articles

Discriminating between Metallic and Semiconducting Single-Walled Carbon Nanotubes Using Physisorbed Adsorbates: Role of Wavelike Charge-Density Fluctuations.

Discriminating between metallic (M) and semiconducting (S) single-walled carbon nanotubes (SWNTs) remains a fundamental challenge in the field of nanotechnology. We address this issue by studying the adsorption of the isotropic atoms Xe, Kr, and a highly anisotropic molecule n heptane on M- and S-SWNTs with density functional theory that includes many-body dispersion forces. We find that the distinct polarizabilities of M- and S-SWNTs exhibit significantly different physisorption properties, which are also strongly controlled by the SWNT's diameter, adsorption site, adsorbate coverage, and the adsorbate's anisotropy. These findings stem from the wavelike nature of charge-density fluctuations in SWNTs. Particularly, these results allow us to rationalize the unusual sqrt[3]×sqrt[3]R30^{0} phase of Kr atoms on small gap M-SWNTs and the double desorption peak temperatures of n heptane on M-SWNTs in experiments, and also propose the n heptane as an effective sensor for experimentally discriminating M- and S-SWNTs.

Zero-point energy differences and many-body dispersion forces.

The fully retarded dispersion interaction potentials, including many-body interactions, among neutral molecules are found in a systematic way. The method used relates the total zero-point energy of all the electromagnetic modes with the spectral sum of a linear operator. The difference between the zero-point energies with and without the molecules present is given as a contour integral. From the value of this integral it is possible to extract the N-body dispersion energy by locating those terms which depend on the product of the polarizabilities of those N molecules. The Casimir-Polder pairwise energy is the two-body result. General formulas are found, and the special cases for N=3 and 4 are discussed in detail. The nonretarded interaction potentials are found as the asymptotic limits for small intermolecular separations, and the London and the Axilrod-Teller results are the N=2 and N=3 special cases. The N=4 near-zone limit is presented in its explicit form. It is of interest to note that, for the one-body case, the energy shift given by this method is the nonrelativistic Lamb shift.

Theoretical atomic-force-microscopy study of adsorbed fullerene molecules.

The capability of atomic-force microscopy (AFM) to localize both individual adsorbates and aggregates of adsorbed molecules was demonstrated a few years ago. More recently submonolayers of fullerene molecules deposited on a gold Substrate have been imaged using such devices. In this paper, simulations of the atomic force between a thin probe tip and a set of adsorbed molecules is presented. The long-range part of the interaction is determined from a whole self-consistent procedure in which many-body effects are accounted for at all orders. In this description the probe tip interacts with the molecules and the surface through many-body dispersion forces. Short-range interactions are then included by using an atom-atom semiempirical pairwise potential. Simulations of AFM images of C-60 adsorbed molecules are presented in two different modes of imaging: the constant-tip-height mode and the constant-force mode.

Many-body dispersion forces of polarizable clusters and liquids

A system of atoms with embedded Drude dispersion oscillators interacting through dipole–dipole forces is simulated. Using path integrals it is shown that after the coordinates of the dispersion oscillators are integrated out, the atoms interact through many-body dispersion forces to all orders of the dipole–dipole interaction. Simulations are carried out on clusters to see if the presence of many-body forces leads to ground state geometries different from those predicted from two-body potentials. In addition, the polarizability tensor of clusters is determined as a function of cluster size. Simulations are also carried out for fluids to see how many-body forces affect the pair correlation function. Lastly, the long-range interaction between van der Waals clusters is compared with the predictions of a summation over site–site two-body interactions. It is found that many-body forces have only a minor effect on the low energy geometries of van der Waals clusters, a somewhat surprising result given that many-body forces do give an important contribution to surface free energies of clusters and liquids. The vibrational frequencies of the breathing mode decrease by approximately 10%.