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WIREs Comput Mol Sci
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Finding chemical concepts in the Hilbert space: Coupled cluster analyses of noncovalent interactions

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Abstract Noncovalent interactions (NCIs) play a major role in essentially all fields of chemical research. Energy decomposition analysis (EDA) schemes provide in‐depth insights into their nature by decomposing interaction energies into additive contributions, such as electrostatics, polarization, and London dispersion. Although modern local variants of the “gold standard” coupled‐cluster singles and doubles method plus perturbative triples (CCSD(T)) have made it possible to accurately quantify NCIs for relatively large systems, extracting chemically meaningful energy terms from such high level electronic structure calculations has been a long lasting challenge in computational chemistry. This review describes basic principles, interpretative aspects and applications of recently developed coupled cluster‐based EDAs for the analysis of NCIs. The focus is on computationally efficient methods for systems with a few hundred atoms, for example, the recently introduced local energy decomposition analysis. In order to draw connections between different interpretative frameworks, these schemes are compared with other popular approaches for the quantification and analysis of NCIs, such as Symmetry Adapted Perturbation Theory and supermolecular EDAs based on mean‐field as well as correlated approaches. Strengths and limitations of the various techniques are discussed. This article is characterized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Structure and Mechanism > Molecular Structures
Mean absolute deviation (MAD) for the S66 benchmark set for popular exchange correlation functionals with (black bars) and without (gray checkered bars) –D3 correction. The Becke–Johnson damping variant was used in the –D3 correction. The data used in this figure were taken from Reference
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Distance dependence of DLPNO‐CCSD(T)/def2‐TZVP and reference QRO/def2‐TZVP energies for the interaction of CO with the 3A2g triplet (panel a), 3Eg triplet (panel b), and 1A1g singlet (panel c) states of PFe. Data were taken from Reference . For DLPNO‐CCSD(T) binding energies with larger basis sets the reader is referred to Reference
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Left: Binding energy profiles for the Re⋯CH4 interaction in [CpRe(CO)2(CH4)]computed at the DLPNO‐CCSD(T)/def2‐TZVPP and HF/def2‐TZVPP level of theory as a function of the inter‐fragment distance. Data were taken from Reference . Right: DLPNO‐CCSD(T)/def2‐QZVP HF and HF/def2‐QZVP energy profiles associated to the rotation of the agostic methyl group around the Cα─Cβ bond in the agostic [EtTiCl3(dmpe)] (dmpe = 1,2‐bis(dimethylphosphino)ethane). The reference energy corresponds to the equilibrium geometry (θ = 0). Data were taken from Reference
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Binding energy for various interaction types computed at the DLPNO‐CCSD(T)/CBS and HF/CBS level of theory as a function of the inter‐fragment distance. The vertical line represents the correlation contribution to the interaction energy and the London dispersion component is reported in red. The red cross denotes the experimental value. (a) The dispersion dominated Ar─Ar interaction. (b) The polarization (induction) dominated Ar─Li+ interaction. (c) The “electron‐sharing”‐dominated Be─Be interaction. (d) The electrostatically dominated interaction in the water dimer. Data were taken from Reference
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Double excitation types involving more than two fragments
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Classes of double excitation contributions in which the correlation energy can be decomposed in post‐HF EDA schemes. X and Y denote the fragments
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Binding energies for a frustrated Lewis pair computed using various DFT and DFT‐D3 functionals. The Lewis acid is B(C6F5)3, the Lewis base is the phosphine P(Mes)3. The contribution from the D3 correction is shown with a red arrow for the two extreme cases. The blue horizontal line represents the benchmark DLPNO‐CCSD(T) value at the complete basis set limit (CBS). Data were taken from Reference
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Structure and Mechanism > Molecular Structures
Electronic Structure Theory > Ab Initio Electronic Structure Methods

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