Recent developments in symmetry‐adapted perturbation theory

Patkowski, Konrad

doi:10.1002/wcms.1452

Cited by 137 publications

(147 citation statements)

References 427 publications

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“…Thanks to this new development, the entire SAPT0 level of theory (but not higher levels such as second-order, SAPT2) is now available in Psi4 without the single-exchange approximation. Preliminary numerical tests show [157][158][159] that the replacement of E (20) exch−disp (S 2 ) by its nonapproximated counterpart introduces inconsequential changes to the SAPT0 interaction potentials at short intermolecular separations. In contrast, the full E range, especially for interactions involving ions.…”

Section: E Sapt0 Without the Single-exchange Approximationmentioning

confidence: 99%

PSI4 1.4: Open-source software for high-throughput quantum chemistry

Smith

Burns

Simmonett

et al. 2020

The Journal of Chemical Physics

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537

479

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Psi4 is a free and open-source ab initio electronic structure program providing Hartree-Fock, density functional theory, many-body perturbation theory, configuration interaction, density cumulant theory, symmetry-adapted perturbation theory, and coupled-cluster theory. Most of the methods are quite efficient thanks to density fitting and multi-core parallelism. The program is a hybrid of C++ and Python, and calculations may be run with very simple text files or using the Python API, facilitating post-processing and complex workflows; method developers also have access to most of Psi4's core functionality via Python. Job specification may be passed using The Molecular Sciences Software Institute (MolSSI) QCSchema data format, facilitating interoperability. A rewrite of our top-level computation driver, and concomitant adoption of the MolSSI QCArchive Infrastructure project, make the latest version of Psi4 well suited to distributed computation of large numbers of independent tasks. The project has fostered the development of independent software components that may be reused in other quantum chemistry programs. File list (2) download file view on ChemRxiv psi4.pdf (4.37 MiB) download file view on ChemRxiv supplementary_material.pdf (297.86 KiB)

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Section: E Sapt0 Without the Single-exchange Approximationmentioning

confidence: 99%

PSI4 1.4: Open-source software for high-throughput quantum chemistry

Smith

Burns

Simmonett

et al. 2020

The Journal of Chemical Physics

Self Cite

537

479

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“…The second-order dispersion energies calculated in this work include both the polarization and exchange components. We use the E DISP (2) notation for the energy terms calculated directly within the SAPT 49 , 50 framework …”

Section: Computational Detailsmentioning

confidence: 99%

“…Being able to explicitly calculate the E DISP MC contribution, we propose the “CAS plus dispersion” approach which strictly avoids the double counting of the dispersion contribution and recovers the total interaction energy as where E int MC is the supermolecular interaction energy obtained within the assumed WFT and E DISP (2) is the full second-order dispersion energy. We present the results for wave functions of the CAS type and use the symmetry-adapted perturbation theory (SAPT) 49 , 50 to obtain the E DISP (2) energy contributions.…”

Section: Introductionmentioning

confidence: 99%

How Much Dispersion Energy Is Included in the Multiconfigurational Interaction Energy?

Hapka

Krzemińska

Pernal

2020

J. Chem. Theory Comput.

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We demonstrate how to quantify the amount of dispersion interaction recovered by supermolecular calculations with the multiconfigurational self-consistent field (MCSCF) wave functions. For this purpose, we present a rigorous derivation which connects the portion of dispersion interaction captured by the assumed wave function model—the residual dispersion interaction—with the size of the active space. Based on the obtained expression for the residual dispersion contribution, we propose a dispersion correction for the MCSCF that avoids correlation double counting. Numerical demonstration for model four-electron dimers in both ground and excited states described with the complete active space self-consistent field (CASSCF) reference serves as a proof-of-concept for the method. Accurate results, largely independent of the size of the active space, are obtained. For many-electron systems, routine CASSCF interaction energy calculations recover a tiny fraction of the full second-order dispersion energy. We found that the residual dispersion is non-negligible only for purely dispersion-bound complexes.

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“…An alternative theoretical approach for computing the interaction energy is symmetry adapted perturbation theory (SAPT). [22][23][24] In its wavefunction-based formulation, SAPT accounts for the interaction between two monomer Hartree-Fock wavefunctions through a triple perturbation series in monomer A correlation, monomer B correlation, and intermonomer interaction. SAPT has a few advantages over the supermolecular approach.…”

Section: A Symmetry Adapted Perturbation Theorymentioning

confidence: 99%

AP-Net: An Atomic-Pairwise Neural Network for Smooth and Transferable Interaction Potentials

Glick

Metcalf²,

Koutsoukas³

et al. 2020

Preprint

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<div> <div> <div> <p>Intermolecular interactions are critical to many chemical phenomena, but their accurate computation using <i>ab initio</i> methods is often limited by computational cost. The recent emergence of machine learning (ML) potentials may be a promising alternative. Useful ML models should not only estimate accurate interaction energies, but also predict smooth and asymptotically correct potential energy surfaces. However, existing ML models are not guaranteed to obey these constraints. Indeed, systemic deficiencies are apparent in the predictions of our previous hydrogen-bond model as well as the popular ANI-1X model, which we attribute to the use of an atomic energy partition. As a solution, we propose an alternative atomic-pairwise framework specifically for intermolecular ML potentials, and we introduce AP-Net—a neural network model for interaction energies. The AP-Net model is developed using this physically motivated atomic-pairwise paradigm and also exploits the interpretability of symmetry adapted perturbation theory (SAPT). We show that in contrast to other models, AP-Net produces smooth, physically meaningful intermolecular potentials exhibiting correct asymptotic behavior. Initially trained on only a limited number of mostly hydrogen-bonded dimers, AP-Net makes accurate predictions across the chemically diverse S66x8 dataset, demonstrating significant transferability. On a test set including experimental hydrogen-bonded dimers, AP-Net predicts total interaction energies with a mean absolute error of 0.37 kcal mol−1, reducing errors by a factor of 2-5 across SAPT components from previous neural network potentials. The pairwise interaction energies of the model are physically interpretable, and an investigation of predicted electrostatic energies suggests that the model ‘learns’ the physics of hydrogen-bonded interactions. </p> </div> </div> </div>

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Recent developments in symmetry‐adapted perturbation theory

Cited by 137 publications

References 427 publications

PSI4 1.4: Open-source software for high-throughput quantum chemistry

PSI4 1.4: Open-source software for high-throughput quantum chemistry

How Much Dispersion Energy Is Included in the Multiconfigurational Interaction Energy?

AP-Net: An Atomic-Pairwise Neural Network for Smooth and Transferable Interaction Potentials

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