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Issue 24, 2006
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A fast correlated electronic structure method for computing interaction energies of large van der Waals complexes applied to the fullereneporphyrin dimer

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Abstract

A new implementation of the scaled opposite spin Møller–Plesset (SOS-MP2) method is briefly described, which exploits the locality and sparsity of expansion coefficients and as a result has computational costs that increase approximately quadratically with molecular size. The performance of SOS-MP2 for describing stacked π-complexes is carefully investigated using the benzene, ethylene, uracil, and naphthalene dimers as model systems. It is demonstrated that counterpoise-corrected SOS-MP2 results, extrapolated towards the complete basis set (CBS) limit using a two-point extrapolation scheme, can yield association energies that are reasonably close to the best available numbers, when the single scale factor is chosen as 1.55 for extrapolating results at the cc-pVDZ and cc-pVTZ levels. This methodology yields an interaction energy for the fullerene–tetraphenylporphyrin dimer of −31.47 kcal mol−1 while Hartree–Fock (HF) with the cc-pVTZ basis finds the dimer at the same geometry is unbound by +10.83 kcal mol−1. This implies that the net binding is a result of substantial correlation effects, presumably long-range London dispersions.

Graphical abstract: A fast correlated electronic structure method for computing interaction energies of large van der Waals complexes applied to the fullerene–porphyrin dimer

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Publication details

The article was received on 17 Feb 2006, accepted on 09 May 2006 and first published on 26 May 2006


Article type: Paper
DOI: 10.1039/B602438F
Citation: Phys. Chem. Chem. Phys., 2006,8, 2831-2840
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    A fast correlated electronic structure method for computing interaction energies of large van der Waals complexes applied to the fullereneporphyrin dimer

    Y. Jung and M. Head-Gordon, Phys. Chem. Chem. Phys., 2006, 8, 2831
    DOI: 10.1039/B602438F

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