Accurate dipole polarizabilities for water clusters n = 2–12 at the coupled-cluster level of theory and benchmarking of various density functionals

Hammond, Jeff R.; Govind, Niranjan; Kowalski, Karol; Autschbach, Jochen; Xantheas, Sotiris S.

doi:doi:10.1063/1.3263604

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The static dipole polarizabilities of water clusters (2 ≤ N ≤ 12) are determined at the coupled-cluster level of theory (CCSD). For the dipole polarizability of the water monomer it was determined that the role of the basis set is more important than that of electron correlation and that the basis set augmentation converges with two sets of diffuse functions. The CCSD results are used to benchmark a variety of density functionals while the performance of several families of basis sets (Dunning, Pople, and Sadlej) in producing accurate values for the polarizabilities was also examined. The Sadlej family of basis sets was found to produce accurate results when compared to the ones obtained with the much larger Dunning basis sets. It was furthermore determined that the PBE0 density functional with the aug-cc-pVDZ basis set produces overall remarkably accurate polarizabilities at a moderate computational cost.

Article Outline

INTRODUCTION
COMPUTATIONAL DETAILS
RESULTS
1. Electron correlation and basis set effects for the polarizability of the water monomer and dimer
2. Accurate polarizabilities of water clusters n = 1–4
3. Benchmarking of various families of basis sets for computing water cluster polarizabilities
4. Benchmarking of various density functionals for computing water cluster polarizabilities
CONCLUSIONS

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KEYWORDS and PACS

Keywords

coupled cluster calculations, density functional theory, electron correlations, molecular clusters, polarisability, water

PACS

33.15.Kr

Electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility
36.40.Cg

Electronic and magnetic properties of clusters
31.15.bw

Coupled-cluster theory
31.15.E-

Density-functional theory
31.15.V-

Electron correlation calculations for atoms, ions and molecules

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http://dx.doi.org/10.1063/1.3263604

PUBLICATION DATA

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0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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