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Given the omnipresence
of noncovalent interactions (NCIs), their
accurate simulations are of crucial importance across various scientific
disciplines. Here we construct accurate models for the description
of NCIs by an interpolation along the Møller–Plesset adiabatic
connection (MP AC). Our interpolation approximates the correlation
energy, by recovering MP2 at small coupling strengths and the correct
large-coupling strength expansion of the MP AC, recently shown to
be a functional of the Hartree–Fock density. Our models are
size consistent for fragments with nondegenerate ground states, have
the same cost as double hybrids, and require no dispersion corrections
to capture NCIs accurately. These interpolations greatly reduce large
MP2 errors for typical π-stacking complexes (e.g., benzene–pyridine
dimers) and for the L7 data set. They are also competitive with state-of-the-art
dispersion enhanced functionals and can even significantly outperform
them for a variety of data sets, such as CT7 and L7.
We have studied the correlation potentials produced by various adiabatic connection models (ACM) for several atoms and molecules. The results have been compared to accurate reference potentials (coupled cluster and quantum Monte Carlo results) as well as to state-of-theart ab initio DFT approaches. We have found that all the ACMs yield correlation potentials that exhibit a correct behavior, quite resembling scaled second-order Görling-Levy (GL2) potentials, and including most of the physically meaningful features of the accurate reference data. The behavior and contribution of the strong-interaction limit potentials has also been investigated and discussed.
While in principle exact, Kohn-Sham density functional theory-the workhorse of computational chemistry-must rely on approximations for the exchange-correlation functional. Despite staggering successes, present-day approximations still struggle when the effects of electron-electron correlation play a prominent role. The limit in which the electronic Coulomb repulsion completely dominates the exchange-correlation functional offers a well-defined mathematical framework that provides insight for new approximations able to deal with strong correlation. In particular, the mathematical structure of this limit, which is now well-established thanks to its reformulation as an optimal transport problem, points to the use of very different ingredients (or features) with respect to the traditional ones used in present approximations. We focus on strategies to use these new ingredients to build approximations for computational chemistry and highlight future promising directions.
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