Benchmark Databases of Intermolecular Interaction Energies: Design, Construction, and Significance

Patkowski, Konrad

doi:10.1016/bs.arcc.2017.06.004

Cited by 17 publications

(12 citation statements)

References 457 publications

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“…Publicly available databases 5 – 14 offer a way to amortize this cost over a large user community, thus reducing the burden on individual researchers. Such databases serve as recognized benchmarks, and are indispensable resources for both accuracy assessment and parameterization of more affordable QM approximations such as exchange-correlation functionals 12 – 17 in the density functional theory framework, empirically corrected wavefunction-based approaches 18 – 23 , and semi-empirical methods 24 – 27 (for a comprehensive review, see summary works 28 , 29 ). Benchmark-quality QM data, often in combination with experimental data, also feature prominently in the development of many empirical molecular mechanics–based models (so-called “force fields”) 30 – 34 .…”

Section: Background and Summarymentioning

confidence: 99%

Quantum chemical benchmark databases of gold-standard dimer interaction energies

et al. 2021

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Advances in computational chemistry create an ongoing need for larger and higher-quality datasets that characterize noncovalent molecular interactions. We present three benchmark collections of quantum mechanical data, covering approximately 3,700 distinct types of interacting molecule pairs. The first collection, which we refer to as DES370K, contains interaction energies for more than 370,000 dimer geometries. These were computed using the coupled-cluster method with single, double, and perturbative triple excitations [CCSD(T)], which is widely regarded as the gold-standard method in electronic structure theory. Our second benchmark collection, a core representative subset of DES370K called DES15K, is intended for more computationally demanding applications of the data. Finally, DES5M, our third collection, comprises interaction energies for nearly 5,000,000 dimer geometries; these were calculated using SNS-MP2, a machine learning approach that provides results with accuracy comparable to that of our coupled-cluster training data. These datasets may prove useful in the development of density functionals, empirically corrected wavefunction-based approaches, semi-empirical methods, force fields, and models trained using machine learning methods.

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Section: Background and Summarymentioning

confidence: 99%

Quantum chemical benchmark databases of gold-standard dimer interaction energies

et al. 2021

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“…A common protocol to establish the performance of a method for intermolecular interactions of different nature and strength are calculations on balanced benchmark datasets of noncovalently bound dimers. 131 The first such evaluation of RSHs was presented in Ref. 63.…”

Section: Benchmark Datasets For Noncovalent Interactionsmentioning

confidence: 99%

Range‐separated multiconfigurational density functional theory methods

Pernal

Hapka

2021

WIREs Comput Mol Sci

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Range-separated multiconfigurational density functional theory (RS MC-DFT) rigorously combines density functional (DFT) and wavefunction (WFT) theories. This is achieved by partitioning of the electron interaction operator into long-and short-range components and modeling them with WFT and DFT, respectively. In contrast to other methods, mixing wavefunctions with density functionals, RS MC-DFT is free from electron correlation double counting. The general formulation of RS MC-DFT allows for merging any ab initio approximation with density functionals. Implementations of RS MC-DFT aim at increasing both versatility and accuracy of the underlying methods, while reducing the computational cost of the ab initio problem. Variants of the RS MC-DFT approach can be divided into single-determinant-based range-separated methods and range-separated multideterminantal WFT methods. In these approaches the electron correlation energy is described both by a pertinent short-range density functional and by the wavefunction theory. We review the short-range functionals and correlated wavefunction theories employed in the framework of RS MC-DFT. We discuss applications of the RS MC-DFT methods to ground-state properties of molecules and to noncovalent interactions. Time-dependent linear-response theory and direct approaches to excited states are also presented. For each area of applications, we assess advantages of RS MC-DFT over conventional DFT and ab initio methods.

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“…In contrast to the rich toolbox dedicated to single-determinantal wave functions, 12 , 13 describing intermolecular interactions in complexes that demand multiconfigurational (MC) wave functions presents a challenge. The multiconfigurational treatment is often mandatory for transition-metal complexes, open-shell systems, electronically excited states, or systems dominated by static correlation effects.…”

Section: Introductionmentioning

confidence: 99%

Symmetry-Adapted Perturbation Theory Based on Multiconfigurational Wave Function Description of Monomers

Hapka

Przybytek

Pernal

2021

J. Chem. Theory Comput.

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We present a formulation of the multiconfigurational (MC) wave function symmetry-adapted perturbation theory (SAPT). The method is applicable to noncovalent interactions between monomers which require a multiconfigurational description, in particular when the interacting system is strongly correlated or in an electronically excited state. SAPT(MC) is based on one- and two-particle reduced density matrices of the monomers and assumes the single-exchange approximation for the exchange energy contributions. Second-order terms are expressed through response properties from extended random phase approximation (ERPA). The dispersion components of SAPT(MC) have been introduced in our previous works [ Hapka M. Hapka M. 30525591 J. Chem. Theory Comput. 2019 15 1016 1027 ; Hapka M. Hapka M. 31670950 J. Chem. Theory Comput. 2019 15 6712 6723 ]. SAPT(MC) is applied either with generalized valence bond perfect pairing (GVB) or with complete active space self-consistent field (CASSCF) treatment of the monomers. We discuss two model multireference systems: the H 2 ··· H 2 dimer in out-of-equilibrium geometries and interaction between the argon atom and excited state of ethylene. Using the C 2 H 4 * ··· Ar complex as an example, we examine second-order terms arising from negative transitions in the linear response function of an excited monomer. We demonstrate that the negative-transition terms must be accounted for to ensure qualitative prediction of induction and dispersion energies and develop a procedure allowing for their computation. Factors limiting the accuracy of SAPT(MC) are discussed in comparison with other second-order SAPT schemes on a data set of small single-reference dimers.

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Benchmark Databases of Intermolecular Interaction Energies: Design, Construction, and Significance

Cited by 17 publications

References 457 publications

Quantum chemical benchmark databases of gold-standard dimer interaction energies

Quantum chemical benchmark databases of gold-standard dimer interaction energies

Range‐separated multiconfigurational density functional theory methods

Symmetry-Adapted Perturbation Theory Based on Multiconfigurational Wave Function Description of Monomers

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