The Role of Bond Functions in Describing Intermolecular Electron Correlation for Van der Waals Dimers: A Study of (CH4)2 and Ne2.

We present a study of the intermolecular interactions in van der Waals complexes of methane and neon dimers within the framework of the CCSD method. This approach was implemented and applied to calculate and examine the behavior of the contracted two-particle reduced density matrix (2-RDM). It was demonstrated that the region near the minimum of the two-particle density matrix correlation part, corresponding to the primary bulk of the Coulomb hole contribution, exerts a significant influence on the dispersion interaction energetics of the studied systems. As a result, the bond functions approach was applied to improve the convergence performance for the intermolecular correlation energy results with respect to the size of the atomic basis. For this, substantial acceleration was achieved by introducing an auxiliary basis of bond functions centered on the minima of the 2-RDM. For both methane and neon dimers, this general conclusion was confirmed with a series of CCSD calculations for the 2-RDM and the correlation energies.

Accommodation of a dimer in an Ar-like lattice: exploring the generic structural motifs.

A global optimization strategy is applied to Lennard-Jones models describing the stable trapping sites of a dimer in the face-centered cubic Ar-like lattice. Effective volumes of the trapping sites, quantified as the number of host atoms dislodged from the lattice, are mapped onto the parameter space defined by the strength and range of the dimer interaction potentials. The two models considered differ in the host-guest interaction and give very different maps that reflect the effect of local lattice relaxation. A hierarchical complete-linkage clustering technique is applied to identify generic structural types of the dimer accommodations. The dominant types found and enlisted maintain the symmetry of the isolated dimer and possess high tetrahedral and octahedral symmetry of the host environment with respect to the dimer atoms or center and can be roughly classified as the "whole" or "per atom" dimer accommodations. The results are compared to the analysis of the analogous model for trapped atoms and realistic model for trapped alkaline-earth metal dimers. Implications for matrix isolation spectroscopy are discussed.