SAPT codes for calculations of intermolecular interaction energies

Garcia, Javier; Podeszwa, Rafał; Szalewicz, Krzysztof

doi:10.1063/5.0005093

Cited by 54 publications

(51 citation statements)

References 242 publications

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“…A feasible path to reduce the scaling and increase the efficiency of the method with no damage to the accuracy involves density fitting or Cholesky decomposition techniques routinely applied in single-reference SAPT approaches. 81,85,97,[128][129][130][131]…”

Section: Discussionmentioning

confidence: 99%

Symmetry-adapted perturbation theory based on multiconfigurational wave function description of monomers

Hapka¹,

Przybytek²,

Pernal³

2021

Preprint

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We present a formulation of the multiconfigurational (MC) wave function symmetryadapted 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) equations. 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. In both cases SAPT(MC) closely reproduces benchmark results. 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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Section: Discussionmentioning

confidence: 99%

Symmetry-adapted perturbation theory based on multiconfigurational wave function description of monomers

Hapka¹,

Przybytek²,

Pernal³

2021

Preprint

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“…Second is the Pauli (exchange) repulsion, which arises when antisymmetrizing the wave function of the complete system. 42 In molecular force fields, dispersion and Pauli repulsion are often considered together as one van der Waals potential, traced back to Lennard-Jones. 43 A comprehensive historical summary of the subject was published recently.…”

Section: Dispersion;mentioning

confidence: 99%

Comparison of approximate intermolecular potentials for ab initio fragment calculations on medium sized N‐heterocycles

et al. 2022

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The ground state intermolecular potential of bimolecular complexes of N‐heterocycles is analyzed for the impact of individual terms in the interaction energy as provided by various, conceptually different theories. Novel combinations with several formulations of the electrostatic, Pauli repulsion, and dispersion contributions are tested at both short‐ and long‐distance sides of the potential energy surface, for various alignments of the pyrrole dimer as well as the cytosine–uracil complex. The integration of a DFT/CCSD density embedding scheme, with dispersion terms from the effective fragment potential (EFP) method is found to provide good agreement with a reference CCSD(T) potential overall; simultaneously, a quantum mechanics/molecular mechanics approach using CHELPG atomic point charges for the electrostatic interaction, augmented by EFP dispersion and Pauli repulsion, comes also close to the reference result. Both schemes have the advantage of not relying on predefined force fields; rather, the interaction parameters can be determined for the system under study, thus being excellent candidates for ab initio modeling.

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“…While aiFFs have been used in CSPs for some time 19 , 32 – 34 , such predictions were taking a long time (several months at the minimum), required huge amounts of human effort, and were possible for monomers with up to about 20 atoms. In the present work, four recent developments are combined to dramatically reduce costs and increase predictability of such CSPs: (a) The development of a very effective variant 35 of symmetry-adapted perturbation theory (SAPT) 36 for ab initio calculations of interaction energies; (b) The creation of autoPES 37 , 38 : an automatic, effective, and reliable method for generation of potential energy surfaces (PESs) with minimal human involvement; (c) Enabling the use such aiFFs in the lattice-energy minimization stage of CSPs, a part of the present work; (d) The application of pDFT+D for a final refinement of polymorph rankings. Stage 3 of Fig.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, both the ab initio method and the fit to interaction energies computed using this method must have sufficiently small uncertainties. In calculations of dimer interaction energies, the variant of SAPT used by us (see “Methods”) is nearly as accurate 35 , 42 , 43 as the coupled cluster method with single, double, and noniterative triple excitations, CCSD(T), the “gold-standard” method of electronic structure theory, but is significantly less expensive. To prevent loss of accuracy due to fitting, the form of the fitting function has to be significantly more involved than those of empirical FFs that are typically built from Lennard-Jones plus Coulomb potentials, see “Methods”.…”

Section: Introductionmentioning

confidence: 99%

Reliable crystal structure predictions from first principles

Nikhar

Szalewicz

2022

Nat Commun

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An inexpensive and reliable method for molecular crystal structure predictions (CSPs) has been developed. The new CSP protocol starts from a two-dimensional graph of crystal’s monomer(s) and utilizes no experimental information. Using results of quantum mechanical calculations for molecular dimers, an accurate two-body, rigid-monomer ab initio-based force field (aiFF) for the crystal is developed. Since CSPs with aiFFs are essentially as expensive as with empirical FFs, tens of thousands of plausible polymorphs generated by the crystal packing procedures can be optimized. Here we show the robustness of this protocol which found the experimental crystal within the 20 most stable predicted polymorphs for each of the 15 investigated molecules. The ranking was further refined by performing periodic density-functional theory (DFT) plus dispersion correction (pDFT+D) calculations for these 20 top-ranked polymorphs, resulting in the experimental crystal ranked as number one for all the systems studied (and the second polymorph, if known, ranked in the top few). Alternatively, the polymorphs generated can be used to improve aiFFs, which also leads to rank one predictions. The proposed CSP protocol should result in aiFFs replacing empirical FFs in CSP research.

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SAPT codes for calculations of intermolecular interaction energies

Cited by 54 publications

References 242 publications

Symmetry-adapted perturbation theory based on multiconfigurational wave function description of monomers

Symmetry-adapted perturbation theory based on multiconfigurational wave function description of monomers

Comparison of approximate intermolecular potentials for ab initio fragment calculations on medium sized N‐heterocycles

Reliable crystal structure predictions from first principles

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