Performance of spin-component-scaled Møller–Plesset theory (SCS-MP2) for potential energy curves of noncovalent interactions

Takatani, Tait; Sherrill, C. David

doi:10.1039/b709669k

Cited by 112 publications

(113 citation statements)

References 41 publications

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“…44 In Table 2 we show the CCSD (T)/CBS binding energies of the J conformer using the aug-cc-pVXZ basis sets. These CCSD(T)/CBS energies are also consistent with the benchmark potential data in the literature, 25,28 where the focal point approximation was Table 2. The estimated CCSD(T) binding energies in kcal/mol at the complete basis set limit using the four extrapolation methods mentioned in the text used.…”

Section: Methods and Force Field Constructionsupporting

confidence: 84%

A Refined Intermolecular Interaction Potential for Methane: Spectral Analysis and Molecular Dynamics Simulations

Li¹,

Chao

2016

J Chinese Chemical Soc

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The previously constructed methane interaction potential energy surface calculated at the second-order Møller-Plesset (MP2) perturbation theory has been significantly improved in two aspects. First, all ab initio potential energy data are calculated by the supermolecule counterpoise corrected coupled cluster with single and double and perturbative triple excitations [CCSD(T)] method with Dunning's correlation-consistent aug-cc-pVXZ, X = D, T, Q, 5, basis sets and extrapolated to the complete basis set (CBS) limits with a convergence precision of 0.01 kcal/mol. Second, instead of the simple 4-site model proposed in the previous study, a 5-site model has been used to represent the ab initio potential data. The simulated infrared spectrum using the potential energy surface seems to be broadly in line with the spectral features observed in experiments. Molecular dynamics simulations using the ab initio force field show quantitative agreements with experiments. The properties examined in this paper include the atom-to-atom radial distribution functions in liquid and supercritical phases and the self-diffusion coefficients over a wide range of thermodynamic conditions. It is shown that the refined ab initio force field can be applied to study fluid properties in different phases.

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Section: Methods and Force Field Constructionsupporting

confidence: 84%

A Refined Intermolecular Interaction Potential for Methane: Spectral Analysis and Molecular Dynamics Simulations

Li¹,

Chao

2016

J Chinese Chemical Soc

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“…Finally, we optimized the geometry of the methane dimer in the D 3d conformation using LCS-VV09 and computational details as in Table II. LCS-VV09 predicts the equilibrium C-C distance of 3.8 Å and the binding energy of 0:54 kcal=mol, which agree well with the reference values [25] of 3.6 Å and 0:54 kcal=mol.…”

Section: Prl 103 063004 (2009) P H Y S I C a L R E V I E W L E T T Esupporting

confidence: 69%

Nonlocal van der Waals Density Functional Made Simple

2009

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We derive a nonlocal correlation functional that adequately describes van der Waals interactions not only in the asymptotic long-range regime but also at short range. Unlike its precursor, developed by Langreth, Lundqvist, and co-workers, the new functional has a simple analytic form, finite for all interelectron separations, well behaved in the slowly varying density limit, and generalized to spinpolarized systems. DOI: 10.1103/PhysRevLett.103.063004 PACS numbers: 31.15.EÀ, 34.20.Gj, 71.15.Mb Kohn-Sham density functional theory (DFT) [1] is the most prominent method for the electronic structure of molecules and solids, but commonly used semilocal correlation functionals completely miss nonlocal dispersion interactions [2]. This is a significant flaw, since dispersion (van der Waals) forces [3] are essential for the formation and properties of biological macromolecules, nanostructures, molecular crystals, polymers, liquids, and other types of sparse matter. The search for dispersion corrections amending common functionals is the subject of immense current interest. Considerable success has been achieved with empirical corrections in the form of force fields (see reviews in Refs. [2,4]). Among the pure DFT methods, the nonlocal correlation functional of Ref.[5] is unique, because it was derived from first principles, describes dispersion interactions in a general and seamless fashion, and yields the correct asymptotics (at least for nonconductors). Applications of this van der Waals density functional (vdW-DF-04) to various weakly bound systems are reviewed in Ref. [6]. vdW-DF-04 is known to be incompatible [7,8] with accurate exchange functionals, i.e., with Hartree-Fock (HF) or long-range corrected (LC) hybrid exchange models. Recently, we proposed [9] a modification, denoted vdW-DF-09, that was adjusted to work well with HF and LC exchange.In this Letter, we derive a new correlation functional (which we call VV09) based on the vdW-DF methodology but incorporating different exact constraints. The VV09 nonlocal correlation energy is expressed in a straightforward analytic form, whereas its predecessors (vdW-DF-04 and vdW-DF-09) used numerically tabulated kernels. Furthermore, these predecessors were defined only for closed-shell systems, but VV09 can treat open-shell systems as well. VV09 correlation performs well in combination with HF or LC exchange.The central quantity in the vdW-DF formalism [5,10] is the polarization operator Sð!Þ, dependent on frequency ! and related to the dielectric function viawhere is the coupling constant, multiplying every occurrence of e 2 inside . To a good approximation, % 1 þ ð À 1Þ, where with no subscript uses ¼ 1. Then Eq. (1) givesThe nonlocal correlation energy is most conveniently expressed [5] in terms of the Fourier transform of S:whereq ¼ q=q is a unit wave vector and P q;q 0 stands for RR dqdq 0 ð2 Þ À6 . Using S ¼ ln in Eq. (3) proves intractable. By the mean value theorem, the integral in Eq. (2) can be replaced bywhere 0 1. It can be shown [9,10] that, in the lim...

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“…We find that XYGJ-OS is remarkably accurate for a broad range of systems and important chemical properties (1,2,(41)(42)(43)(44)(45) other than HOF which are not used in fitting the parameters. Table 1 (more details are in SI Text) compares the overall performance of some representative DFT methods, showing that XYGJ-OS is the best or nearly best for essentially all properties, leading to chemical accuracy (1.28 kcal∕mol) comparable to the G3 theory (which contains four empirical parameters involving the number of electron pairs) (1.06) and much better than MP2 (7.49 kcal∕mol).…”

Section: Resultsmentioning

confidence: 99%

A fast doubly hybrid density functional method close to chemical accuracy using a local opposite spin ansatz

Zhang

Jung

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

157

189

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We develop and validate the XYGJ-OS functional, based on the adiabatic connection formalism and Görling-Levy perturbation theory to second order and using the opposite-spin (OS) ansatz combined with locality of electron correlation. XYGJ-OS with local implementation scales as N 3 with an overall accuracy of 1.28 kcal∕ mol for thermochemistry, bond dissociation energies, reaction barrier heights, and nonbonded interactions, comparable to that of 1.06 kcal∕mol for the accurate coupled-cluster based G3 method (scales as N 7 ) and much better than many popular density functional theory methods: B3LYP (4.98), PBE0 (4.36), and PBE (12.10).btaining chemical accuracy (∼1 kcal∕mol) to quantify key chemical quantities (e.g., heats of formation, bond dissociation energies, and reaction barrier heights) using quantum mechanics (QM) has been a major focus in the development of the theory. This has led to, for example, the Gn method (1, 2) that approaches this chemical accuracy. Because G3 is a coupled-cluster based method, it scales on the order of N 7 , where N measures the system size, limiting to fairly small species for routine use.The desire to predict unique physiochemical phenomena (e.g., solvation, catalysis, self-assembly, and drug design) in practical (large) systems has brought about a second major focus of theoretical development, leading, for example, to divide-and-conquer formulations to attain more efficient scaling (3), but with much lower accuracy than Gn.Density functional theory (DFT) in the framework of KohnSham (KS) scheme (4, 5) provides a "shortcut" to the many-body problem. Many density functional approximations (DFAs), provide typical scaling of N 3 ∼ N 4 , while yielding significantly more accurate results than Hartree-Fock (HF) theory, the lowest level wave function based method with similar scaling, but they still lead to significant errors for some systems. For example, current DFAs lead to a poor description of London dispersion (van der Waals attraction), which is essential to predict the packing of molecules into solids, and the binding of drug molecules to proteins. These DFAs are also poor in predicting the magnitude of reaction barriers.In this article, we develop and present a unique functional, XYGJ-OS, that provides a good combination of high accuracy and speed. XYGJ-OS involves a doubly hybrid density functional (DHDF), containing both a nonlocal orbital-dependent component in the exchange term (HF-like exchange), and also information about the unoccupied KS orbitals in the electron correlation part (PT2, perturbation theory up to second order) using the opposite-spin (OS) ansatz to include the locality of electron correlation. XYGJ-OS provides accuracy comparable to that of Gn for the test datasets and speed with N 2 ∼ N 3 for the local implementation. Hence XYGJ-OS is both accurate and fast. TheoryThe Holy Grail in KS-DFT is to find the exact, yet unknown, exchange-correlation functional E xc ½ρ using density ρ as the basic variable (4, 5). In practice, an approximate E xc must be ado...

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Performance of spin-component-scaled Møller–Plesset theory (SCS-MP2) for potential energy curves of noncovalent interactions

Cited by 112 publications

References 41 publications

A Refined Intermolecular Interaction Potential for Methane: Spectral Analysis and Molecular Dynamics Simulations

A Refined Intermolecular Interaction Potential for Methane: Spectral Analysis and Molecular Dynamics Simulations

Nonlocal van der Waals Density Functional Made Simple

A fast doubly hybrid density functional method close to chemical accuracy using a local opposite spin ansatz

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