Theoretical Chemistry Accounts

, Volume 126, Issue 5, pp 371–382

The optimum contraction of basis sets for calculating spin–spin coupling constants

Regular Article

DOI: 10.1007/s00214-009-0699-5

Cite this article as:
Jensen, F. Theor Chem Acc (2010) 126: 371. doi:10.1007/s00214-009-0699-5

Abstract

The previously proposed pcJ-n basis sets, optimized for calculating indirect nuclear spin–spin coupling constants using density functional methods, are re-evaluated for finding the optimum contraction scheme as a compromise between computational efficiency and minimizing contraction errors. An exhaustive search is performed for the H2, F2 and P2 molecules, and candidates for optimum contraction schemes are evaluated for a larger test set of 21 molecules. Using the criterion that the contraction error should not exceed the basis set error relative to the basis set limit, the optimum contraction is defined for each basis set. The results show that it is difficult to contract basis sets for calculating spin–spin coupling constants to any significant degree without losing the inherent accuracy. The work provides guidelines for searching for optimum contraction schemes for other properties and/or at theoretical levels where a systematic search is impractical.

Keywords

Basis set contractionSpin–spin coupling constantsDFT

Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of AarhusÅrhusDenmark