Local correlation in coupled cluster calculations of molecular response properties

We have extended the local coupled cluster approach of Pulay and Saebo, which has seen great success in the computation of ground-state energies, to molecular response properties such as dipole polarizabilities. This scheme uses an atom-based coupled-perturbed Hartree-Fock breakdown of the desired property to expand the usual ground-state orbital domains. Benchmark tests of the static polarizabilities of helium chains, linear alkanes, and non-saturated systems up to N-acetylglycine indicate that the method can reproduce untruncated coupled cluster properties to within 1% given appropriately chosen cutoffs, even without including orbital relaxation in the method. The method requires increased computational demands, but crossover points between non-local and local approaches are still well within reach of production-level implementations. (C) 2004 Elsevier B.V. All rights reserved.