The limitations of certain density functionals in modeling neutral water clusters

ACS Citation

Shields, G. C.; Kirschner, K. N. The Limitations of Certain Density Functionals in Modeling Neutral Water Clusters. Synth. React. Inorganic, Met. Nano-Metal Chem. 2008, 38 (1), 32-€“36.

Abstract

We have used density functional theory (DFT) with four different functionals and with basis sets optimized for studying water clusters to calculate the structures and energies for selected water dimer, trimer, tetramer, pentamer, hexamer, and octamer structures. We compare the results to the CBS-APNO and G3 model chemistry methods, and with highly accurate MP2 complete basis set limit energies. We find that while all the DFT methods capture the minimum energy structures for tetramers and pentamers, and reproduce the interaction energies well, they fail to find certain structures where London dispersion forces are critical to the interaction. Specifically structures that are not composed of cyclic rings, such as the tetramer pyramid and the pentamer cage structures, are not minima on the DFT potential energy hypersurfaces.

Source Name

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry

Publication Date

2008

Volume

38

Issue

1

Page(s)

32-36

Document Type

Citation

Citation Type

Article

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