Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies

Parker, Trent M.; Burns, Lori A.; Parrish, Robert M.; Ryno, Alden G.; Sherrill, C. David

doi:10.1063/1.4867135

Cited by 735 publications

(887 citation statements)

References 59 publications

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“…Generally, this approximation is very good, although it tends to break down for charged systems at close distances. [148][149][150] This failure can be overcome by scaling the exchange contribution 80 or by completely abandoning the S 2 approximation. 151 Overall, SAPT's lack of versatility remains perhaps its only true weakness.…”

Section: Applying Pt-based Edasmentioning

confidence: 99%

“…The basis set superposition error 79 (BSSE) also becomes problematic. Conversely, that same supermolecularity prevents the theory from breaking down for strong interactions, such as doubly hydrogen bonded systems 80 and, recently, permitted the formulation of "adiabatic EDA," which directly investigates the influence of different interaction types on structural and other molecular properties. 81 …”

Section: Figmentioning

confidence: 99%

“…The components also sum to the total interaction energy, which means they can be systematically improved through the expansion of the interaction operator and the intramonomer correlation operator. 80 The greatest asset of SAPT is certainly its ability to quantify dispersion at all ranges (see Box 2), including regions of overlapping electron density. Generally, SAPT weights dispersion more heavily than other approaches (for example, see the water and benzene dimer examples presented in Figs.…”

Section: A Energy Components In Saptmentioning

confidence: 99%

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Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

111

102

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Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

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Section: Applying Pt-based Edasmentioning

confidence: 99%

Section: Figmentioning

confidence: 99%

Section: A Energy Components In Saptmentioning

confidence: 99%

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Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

111

102

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“…The closed shell calculations were performed by symmetry-adapted perturbation theory as described in ref. 26 and using the aug-cc-pVTZ basis set (27); additional details are in Figs. S5 and S6 (28).…”

Section: Spin Polarization and Enantioselectivitymentioning

confidence: 99%

Chirality-induced spin polarization places symmetry constraints on biomolecular interactions

Kumar

Capua

Kesharwani

et al. 2017

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

185

247

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Noncovalent interactions between molecules are key for many biological processes. Necessarily, when molecules interact, the electronic charge in each of them is redistributed. Here, we show experimentally that, in chiral molecules, charge redistribution is accompanied by spin polarization. We describe how this spin polarization adds an enantioselective term to the forces, so that homochiral interaction energies differ from heterochiral ones. The spin polarization was measured by using a modified Hall effect device. An electric field that is applied along the molecules causes charge redistribution, and for chiral molecules, a Hall voltage is measured that indicates the spin polarization. Based on this observation, we conjecture that the spin polarization enforces symmetry constraints on the biorecognition process between two chiral molecules, and we describe how these constraints can lead to selectivity in the interaction between enantiomers based on their handedness. Model quantum chemistry calculations that rigorously enforce these constraints show that the interaction energy for methyl groups on homochiral molecules differs significantly from that found for heterochiral molecules at van der Waals contact and shorter (i.e., ∼0.5 kcal/mol at 0.26 nm).spin | chirality | enantioselectivity | biorecognition | exchange interaction T he wealth of information on protein structure has led to a much better understanding of the relation between structure and function in biomolecular processes and biological machines (1); however, basic phenomena remain unexplained in terms of structure-function relationships. Biorecognition, which is based on noncovalent interactions between molecules, retains mysteries, and its calculation evades first principles theory (2, 3). This failure suggests that some essential features are not included in our current description of these interactions (4,5). In this study, we show that charge polarization, which occurs in any biorecognition event, is accompanied by spin polarization for chiral molecules, an effect that is missing in most treatments. The subsequent magnetic interaction energies are small and therefore, play no significant role in the interactions; however, the spin polarization constrains the symmetry of the wave function(s) involved with the intermolecular interaction, so that significant differences in energy emerge for interactions between molecules of the same chirality and those of opposite chirality. Thus, this phenomenon may impact quantitative modeling of biorecognition events and contribute to our understanding of enantiorecognition in nature (6).Nucleotides, amino acids, and sugars are chiral; namely, they do not possess mirror plane symmetry but have symmetry like a "hand" (cheir in Greek). Force field models for the interaction between biomolecules do not account for spin polarization or include terms with chiral symmetry. Noncovalent interactions between biomolecules are commonly described classically by way of force fields, which are constructed from their geometrie...

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“…83 The CCSD(T)/CBS energies were computed as the sum of the Hartree-Fock energy in the aug-cc-pVQZ basis set, 37 an MP2 correction extrapolated to the complete basis set limit using Helgaker's formula 84 applied to aug-cc-pVTZ and aug-cc-pVQZ basis sets, 37 and finally a CCSD(T) correction computed with the aug-cc-pVDZ basis set. 37 This procedure corresponds to the one used originally for the S66 dataset.…”

Section: Sapt Energies For the S66x8 Databasementioning

confidence: 99%

The Monomer Electron Density Force Field (MEDFF): A Physically Inspired Model for Noncovalent Interactions

Vandenbrande

Waroquier

Speybroeck

et al. 2016

J. Chem. Theory Comput.

112

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We propose a methodology to derive pairwise-additive non-covalent force fields from monomer electron densities without any empirical input. Energy expressions are based on the Symmetry-Adapted Perturbation Theory (SAPT) decomposition of interaction energies. This ensures a physically motivated force field featuring an electrostatic, exchange-repulsion, dispersion and induction contribution, which contain two types of parameters. First, each contribution depends on several fixed atomic parameters, resulting from a partitioning of the monomer electron density. Second, each of the last three contributions (exchange-repulsion, dispersion and induction) contains exactly one linear fitting parameter. These three so-called interaction parameters in the model, are initially estimated separately using SAPT reference calculations for the S66x8 database of non-covalent dimers. In a second step, the three interaction parameters are further refined simultaneously to reproduce CCSD(T)/CBS interaction energies for the same database. The limited number of parameters that are fitted to 1 dimer interaction energies (only three), avoids ill-conditioned fits that plague conventional parameter optimizations.For the exchange-repulsion and dispersion component, good results are obtained for all dimers in the S66x8 database using one single value for the associated interaction parameters. The values of those parameters can be considered universal and can also be used for dimers not present in the original database used for fitting. For the induction component such an approach is only viable for the dispersion-dominated dimers in the S66x8 database. For other dimers (such as hydrogen-bonded complexes), we show that our methodology remains applicable. However the interaction parameter needs to be determined on a case-specific basis.As an external validation, the force field predicts interaction energies in good agreement with CCSD(T)/CBS values for dispersion-dominated dimers extracted from an HIV-II protease crystal structure with a bound ligand (indinavir). Furthermore, experimental second virial coefficients of small alkanes and alkenes are well reproduced.

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Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies

Cited by 735 publications

References 59 publications

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Chirality-induced spin polarization places symmetry constraints on biomolecular interactions

The Monomer Electron Density Force Field (MEDFF): A Physically Inspired Model for Noncovalent Interactions

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