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WIREs Comput Mol Sci
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Wavefunction methods for noncovalent interactions

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Abstract Noncovalent interactions remain poorly understood despite their importance to supramolecular chemistry, biochemistry, and materials science. They are an ideal target for theoretical study, where interactions of interest can be probed directly, free from competing secondary interactions. However, the most popular tools of computational chemistry are not particularly reliable for noncovalent interactions. Here we review recent works in wavefunction‐based quantum chemistry techniques aimed at greater accuracy and faster computations for these systems. We describe recent developments in high‐accuracy benchmarks, a variety of recent wavefunction methods with promise for noncovalent interactions, various approximations to speed up these methods, and recent advances in wavefunction‐based symmetry‐adapted perturbation theory, which provides not only interaction energies but also their decomposition into physically meaningful components. Together, these advances are currently extending robust, accurate computations of noncovalent interactions from systems with around one dozen heavy atoms up to systems with several dozens of heavy atoms. © 2011 John Wiley & Sons, Ltd. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods

Methane–benzene potential curves computed with various levels of SAPT/aug‐cc‐pVDZ [defined in Eqs (8) and (13)] and with CCSD(T)/aug‐cc‐pVDZ.

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Methane dimer potential energy curves computed with various levels of SAPT/aug‐cc‐pVQZ [defined in Eqs (8) and (13)] and with CCSD(T)/aug‐cc‐pVQZ. The SAPT2+3 and SAPT2+3(CCD) curves are nearly coincident.

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SAPT0/aug‐cc‐pVDZ decomposition of the Na+–benzene interaction. (a) Na+ approaches the center of mass of benzene on a line perpendicular to the plane of the benzene. (b) Na+ approaches the center of mass of benzene in plane with the benzene.

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Parallel‐displaced benzene dimer potential curves computed with various levels of SAPT/aug‐cc‐pVDZ [defined in Eqs (8) and (13)] and with CCSD(T)/aug‐cc‐pVDZ at a vertical separation of 3.6 Å. Although SAPT0 compares poorly to CCSD(T) in this case for a fixed basis set, SAPT0/aug‐cc‐pVDZ′ compares reasonably well with CCSD(T)/CBS estimates due to favorable error cancellation (see Ref 143).

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