Midbond basis functions for weakly bound complexes

ABSTRACT

Weakly bound systems present a difficult problem for conventional atom-centred basis sets due to large separations, necessitating the use of large, computationally expensive bases. This can be remedied by placing a small number of functions in the region between molecules in the complex. We present compact sets of optimised midbond functions for a range of complexes involving noble gases, alkali metals and small molecules for use in high accuracy coupled -cluster calculations, along with a more robust procedure for their optimisation. It is shown that excellent results are possible with double-zeta quality orbital basis sets when a few midbond functions are added, improving both the interaction energy and the equilibrium bond lengths of a series of noble gas dimers by 47% and 8%, respectively. When used in conjunction with explicitly correlated methods, near complete basis set limit accuracy is readily achievable at a fraction of the cost that using a large basis would entail. General purpose auxiliary sets are developed to allow explicitly correlated midbond function studies to be carried out, making it feasible to perform very high accuracy calculations on weakly bound complexes.

KEYWORDS:

• Midbond functions
• explicitly correlated
• noncovalent interactions

Acknowledgments

The authors thank the Engineering and Physical Sciences Research Council (UK) for a postgraduate studentship awarded to Robert A. Shaw and project funding (No. EP/N02253X/1).

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

Engineering and Physical Sciences Research Council [project number EP/N02253X/1].