scholarly journals Application of London Dispersion Corrected Density Functional Theory for Non-Covalent Ion-π Interactions

2020 ◽  
Author(s):  
Eike Caldeweyher ◽  
Sebastian Spicher ◽  
Andreas Hansen ◽  
Stefan Grimme
Keyword(s):  
Electrostatic Interactions ◽  
Density Functional ◽  
Dispersion Model ◽  
Computational Cost ◽  
Coupled Cluster ◽  
Dispersion Interactions ◽  
Field Methods ◽  
Approximate Methods ◽  
London Dispersion ◽  
Pi Interactions

<p>The strongly attractive non-covalent interactions of charged atoms or molecules with pi-systems are important bonding motifs in many chemical and biological systems. These so-called ion-pi interactions play a major role in enzymes, molecular recognition, and for the structure of proteins. To model ion-pi interactions with DFT, it is crucial</p><p>to include London dispersion interactions, whose importance for ion-pi interactions is often underestimated. In this work, several dispersion-corrected DFT methods are evaluated for inter- and intramolecular anionic- and anion-pi interactions in larger and practically relevant molecules. We compare the DFT results with MP2, while highly</p><p>accurate (local) coupled cluster values are provided as reference. The latter can also be a great help in the development and validation of approximate methods. We demonstrate that dispersion-uncorrected DFT underestimates ion-pi interactions significantly, even though electrostatic interactions dominate the overall binding. Accordingly, the</p><p>new charge dependent D4 dispersion model is found to be consistently better than the standard D3 correction. Dispersion-corrected DFT clearly outperforms MP2/CBS whereby the best performers come close to the accuracy limit of the reference values at considerably smaller computational cost. Due to its low cost, D4 can be combined</p><p>very well with semi-empirical QM and force field methods, which is important in the development of more accurate methods for modeling large (bio)chemical systems (e.g. proteins). Another important aspect in modeling these charged systems with DFT is the self-interaction error (SIE). However, we do not find it to constitute a significant problem. Overall, the double hybrid PWPB95-D4/QZ turned out to be the most reliable among all assessed methods in predicting ion-pi interactions, which opens up new perspectives for systems where coupled cluster calculations are no longer computationally feasible.</p>

scholarly journals Application of London Dispersion Corrected Density Functional Theory for Non-Covalent Ion-π Interactions

2020 ◽  
Author(s):  
Eike Caldeweyher ◽  
Sebastian Spicher ◽  
Andreas Hansen ◽  
Stefan Grimme
Keyword(s):  
Electrostatic Interactions ◽  
Density Functional ◽  
Dispersion Model ◽  
Computational Cost ◽  
Coupled Cluster ◽  
Dispersion Interactions ◽  
Field Methods ◽  
Approximate Methods ◽  
London Dispersion ◽  
Pi Interactions

<p>The strongly attractive non-covalent interactions of charged atoms or molecules with pi-systems are important bonding motifs in many chemical and biological systems. These so-called ion-pi interactions play a major role in enzymes, molecular recognition, and for the structure of proteins. To model ion-pi interactions with DFT, it is crucial</p><p>to include London dispersion interactions, whose importance for ion-pi interactions is often underestimated. In this work, several dispersion-corrected DFT methods are evaluated for inter- and intramolecular anionic- and anion-pi interactions in larger and practically relevant molecules. We compare the DFT results with MP2, while highly</p><p>accurate (local) coupled cluster values are provided as reference. The latter can also be a great help in the development and validation of approximate methods. We demonstrate that dispersion-uncorrected DFT underestimates ion-pi interactions significantly, even though electrostatic interactions dominate the overall binding. Accordingly, the</p><p>new charge dependent D4 dispersion model is found to be consistently better than the standard D3 correction. Dispersion-corrected DFT clearly outperforms MP2/CBS whereby the best performers come close to the accuracy limit of the reference values at considerably smaller computational cost. Due to its low cost, D4 can be combined</p><p>very well with semi-empirical QM and force field methods, which is important in the development of more accurate methods for modeling large (bio)chemical systems (e.g. proteins). Another important aspect in modeling these charged systems with DFT is the self-interaction error (SIE). However, we do not find it to constitute a significant problem. Overall, the double hybrid PWPB95-D4/QZ turned out to be the most reliable among all assessed methods in predicting ion-pi interactions, which opens up new perspectives for systems where coupled cluster calculations are no longer computationally feasible.</p>

scholarly journals Benchmarking London dispersion corrected density functional theory for noncovalent ion-pi interactions

2021 ◽  
Author(s):  
Sebastian Spicher ◽  
Eike Caldeweyher ◽  
Andreas Hansen ◽  
Stefan Grimme
Keyword(s):  
Electrostatic Interactions ◽  
Density Functional ◽  
Functional Performance ◽  
Dispersion Model ◽  
Coupled Cluster ◽  
Interaction Energies ◽  
Binding Motifs ◽  
Hybrid Functionals ◽  
London Dispersion ◽  
Pi Interactions

<p>The strongly attractive noncovalent interactions of charged atoms or molecules with p-systems are important binding motifs in many chemical and biological systems. These so-called ion-pi interactions play a major role in enzymes, molecular recognition, and for the structure of proteins. In this work, a molecular test set termed IONPI19 is compiled for inter- and intramolecular ion-pi interactions, which is well balanced between anionic and cationic systems. The IONPI19 set includes interaction energies of significantly larger molecules (up to 133 atoms) than in other ion-pi test sets and covers a broad range of binding motifs. Accurate (local) coupled cluster values are provided as reference. Overall, 18 density functional approximations, including seven (meta-)GGAs, seven hybrid functionals, and four double hybrid functionals combined with three different London dispersion corrections, are benchmarked for interaction energies. DFT results are further compared to wave function based methods such as MP2 and dispersion corrected Hartree-Fock. Also the performance</p><p>of semiempirical QM methods such as the GFNn-xTB and PMx family of methods is tested. It is shown that dispersion-uncorrected DFT underestimates ion-pi interactions significantly, even though electrostatic interactions dominate the overall binding. Accordingly, the new charge dependent D4 dispersion model is found to be consistently better than the standard D3 correction. Furthermore, the functional performance trend along Jacob’s ladder is generally obeyed and the reduction of the self-interaction error leads to an improvement of (double) hybrid functionals over (meta-)GGAs, even though the effect of the SIE is smaller than expected. Overall, the double hybrids PWPB95-D4/QZ and revDSD-PBEP86-D4/QZ turned out to be the most reliable among all assessed methods in predicting ion-pi interactions, which opens up new perspectives for systems where coupled cluster calculations are no longer computationally feasible.</p>

scholarly journals Benchmarking London dispersion corrected density functional theory for noncovalent ion-pi interactions

2021 ◽  
Author(s):  
Sebastian Spicher ◽  
Eike Caldeweyher ◽  
Andreas Hansen ◽  
Stefan Grimme
Keyword(s):  
Electrostatic Interactions ◽  
Density Functional ◽  
Functional Performance ◽  
Dispersion Model ◽  
Coupled Cluster ◽  
Interaction Energies ◽  
Binding Motifs ◽  
Hybrid Functionals ◽  
London Dispersion ◽  
Pi Interactions

<p>The strongly attractive noncovalent interactions of charged atoms or molecules with p-systems are important binding motifs in many chemical and biological systems. These so-called ion-pi interactions play a major role in enzymes, molecular recognition, and for the structure of proteins. In this work, a molecular test set termed IONPI19 is compiled for inter- and intramolecular ion-pi interactions, which is well balanced between anionic and cationic systems. The IONPI19 set includes interaction energies of significantly larger molecules (up to 133 atoms) than in other ion-pi test sets and covers a broad range of binding motifs. Accurate (local) coupled cluster values are provided as reference. Overall, 18 density functional approximations, including seven (meta-)GGAs, seven hybrid functionals, and four double hybrid functionals combined with three different London dispersion corrections, are benchmarked for interaction energies. DFT results are further compared to wave function based methods such as MP2 and dispersion corrected Hartree-Fock. Also the performance</p><p>of semiempirical QM methods such as the GFNn-xTB and PMx family of methods is tested. It is shown that dispersion-uncorrected DFT underestimates ion-pi interactions significantly, even though electrostatic interactions dominate the overall binding. Accordingly, the new charge dependent D4 dispersion model is found to be consistently better than the standard D3 correction. Furthermore, the functional performance trend along Jacob’s ladder is generally obeyed and the reduction of the self-interaction error leads to an improvement of (double) hybrid functionals over (meta-)GGAs, even though the effect of the SIE is smaller than expected. Overall, the double hybrids PWPB95-D4/QZ and revDSD-PBEP86-D4/QZ turned out to be the most reliable among all assessed methods in predicting ion-pi interactions, which opens up new perspectives for systems where coupled cluster calculations are no longer computationally feasible.</p>

A Generally Applicable Atomic-Charge Dependent London Dispersion Correction Scheme

2019 ◽  
Author(s):  
Eike Caldeweyher ◽  
Sebastian Ehlert ◽  
Andreas Hansen ◽  
Hagen Neugebauer ◽  
Sebastian Spicher ◽  
...  
Keyword(s):  
Density Functional ◽  
Dispersion Model ◽  
Low Cost ◽  
Atomic Charge ◽  
Body Part ◽  
Dispersion Interactions ◽  
Dispersion Coefficients ◽  
Charge Dependence ◽  
London Dispersion ◽  
Dynamic Polarizabilities

The D4 model is presented for the accurate computation of London dispersion interactions in density functional theory approximations (DFT-D4) and generally for atomistic modeling methods. In this successor to the DFT-D3 model, the atomic coordination-dependent dipole polarizabilities are scaled based on atomic partial charges which can be taken from various sources. For this purpose, a new charge-dependent parameter-economic scaling function is designed. Classical charges are obtained from an atomic electronegativity equilibration procedure for which efficient analytical derivatives are developed. A numerical Casimir-Polder integration of the atom-in-molecule dynamic polarizabilities yields charge- and geometry-dependent dipole-dipole dispersion coefficients. Similar to the D3 model, the dynamic polarizabilities are pre-computed by time-dependent DFT and elements up to radon are covered. For a benchmark set of 1225 dispersion coefficients, the D4 model achieves an unprecedented accuracy with a mean relative deviation of 3.8% compared to 4.7% for D3. In addition to the two-body part, three-body effects are described by an Axilrod-Teller-Muto term. A common many-body dispersion expansion was extensively tested and an energy correction based on D4 polarizabilities is found to be advantageous for some larger systems. Becke-Johnson-type damping parameters for DFT-D4 are determined for more than 60 common functionals. For various energy benchmark sets DFT-D4 slightly outperforms DFT-D3. Especially for metal containing systems, the introduced charge dependence improves thermochemical properties. We suggest (DFT-)D4 as a physically improved and more sophisticated dispersion model in place of DFT-D3 for DFT calculations as well as for other low-cost approaches like semi-empirical models.<br><br>

A Generally Applicable Atomic-Charge Dependent London Dispersion Correction Scheme

2019 ◽  
Author(s):  
Eike Caldeweyher ◽  
Sebastian Ehlert ◽  
Andreas Hansen ◽  
Hagen Neugebauer ◽  
Sebastian Spicher ◽  
...  
Keyword(s):  
Density Functional ◽  
Dispersion Model ◽  
Low Cost ◽  
Atomic Charge ◽  
Body Part ◽  
Dispersion Interactions ◽  
Dispersion Coefficients ◽  
Charge Dependence ◽  
London Dispersion ◽  
Dynamic Polarizabilities

The D4 model is presented for the accurate computation of London dispersion interactions in density functional theory approximations (DFT-D4) and generally for atomistic modeling methods. In this successor to the DFT-D3 model, the atomic coordination-dependent dipole polarizabilities are scaled based on atomic partial charges which can be taken from various sources. For this purpose, a new charge-dependent parameter-economic scaling function is designed. Classical charges are obtained from an atomic electronegativity equilibration procedure for which efficient analytical derivatives are developed. A numerical Casimir-Polder integration of the atom-in-molecule dynamic polarizabilities yields charge- and geometry-dependent dipole-dipole dispersion coefficients. Similar to the D3 model, the dynamic polarizabilities are pre-computed by time-dependent DFT and elements up to radon are covered. For a benchmark set of 1225 dispersion coefficients, the D4 model achieves an unprecedented accuracy with a mean relative deviation of 3.8% compared to 4.7% for D3. In addition to the two-body part, three-body effects are described by an Axilrod-Teller-Muto term. A common many-body dispersion expansion was extensively tested and an energy correction based on D4 polarizabilities is found to be advantageous for some larger systems. Becke-Johnson-type damping parameters for DFT-D4 are determined for more than 60 common functionals. For various energy benchmark sets DFT-D4 slightly outperforms DFT-D3. Especially for metal containing systems, the introduced charge dependence improves thermochemical properties. We suggest (DFT-)D4 as a physically improved and more sophisticated dispersion model in place of DFT-D3 for DFT calculations as well as for other low-cost approaches like semi-empirical models.<br><br>

scholarly journals A Generally Applicable Atomic-Charge Dependent London Dispersion Correction Scheme

2018 ◽  
Author(s):  
Eike Caldeweyher ◽  
Sebastian Ehlert ◽  
Andreas Hansen ◽  
Hagen Neugebauer ◽  
Sebastian Spicher ◽  
...  
Keyword(s):  
Density Functional ◽  
Dispersion Model ◽  
Atomic Charge ◽  
Body Part ◽  
Dispersion Interactions ◽  
Dispersion Energy ◽  
Dispersion Coefficients ◽  
Charge Dependence ◽  
London Dispersion ◽  
Dynamic Polarizabilities

<div>The so-called D4 model is presented for the accurate computation of London dispersion interactions in density functional theory approximations (DFT-D4) and generally for atomistic modelling methods. In this successor to the DFT-D3 model, the atomic coordination-dependent dipole polarizabilities are scaled based on atomic partial charges which can be taken from various sources. For this purpose, a new charge-dependent parameter-economic scaling function is designed. Classical charges are obtained from an atomic electronegativity equilibration procedure for which efficient analytical derivatives with respect to nuclear positions are developed. A numerical Casimir-Polder integration of the atom-in-molecule dynamic polarizabilities then yields charge- and geometry-dependent dipole-dipole dispersion coefficients. Similar to the D3 model, the dynamic polarizabilities are pre-computed by time-dependent DFT and all elements up to radon (Z = 86) are covered. The two-body dispersion energy expression has the usual sum-over-atom-pairs form and includes dipole-dipole, as well as dipole-quadrupole interactions. For a benchmark set of 1225 molecular dipole-dipole dispersion coefficients, the D4 model achieves an unprecedented accuracy with a mean relative deviation of 3.9% compared to 4.7% for D3. In addition to the two-body part, three-body effects are described by an Axilrod-Teller-Muto term. A common many-body dispersion expansion was extensively tested and an energy correction based on D4 polarizabilities is found to be advantageous for larger systems. Becke-Johnson-type damping parameters for DFT-D4 are determined for more than 60 common density functionals. For various standard energy benchmark sets DFT-D4 slightly but consistently outperforms DFT-D3. Especially for metal containing systems, the introduced charge dependence of the dispersion coefficients improves thermochemical properties. We suggest (DFT-)D4 as a physically improved and more sophisticated dispersion model in place of DFT-D3 for DFT calculations as well as other low-cost approaches like force-fields or semi-empirical models.</div>

scholarly journals Impact of Van der Waals interactions on structural and nonlinear optical properties of azobenzene switches

2021 ◽  
Author(s):  
carmelo Naim ◽  
Frédéric Castet ◽  
Eduard Matito
Keyword(s):  
Density Functional ◽  
Nonlinear Optical ◽  
Van Der Waals Interactions ◽  
Dispersion Interactions ◽  
Geometrical Structures ◽  
Hartree Fock ◽  
Meta Position ◽  
Good Account ◽  
London Dispersion ◽  
Azobenzene Derivatives

<div> <div> <div> <p>The geometrical structures, relative Z-E energies, and second-order nonlinear responses of a collection of azobenzene molecules symmetrically substituted in meta- position with functional groups of different bulkiness are investigated using various ab initio and DFT levels of approximation. We show that RI-MP2 and RI-CC2 approximations provide very similar geometries and relative energies and evidence that London dispersion interactions existing between bulky meta-substituents stabilize the Z con- former. The !B97-X-D exchange-correlation functional provides an accurate description of these effects and gives a good account of the nonlinear optical response of the molecules. We show that density functional approximations should include no less than 50% of Hartree-Fock exchange to provide accurate hyperpolarizabilities. A property-structure analysis of the azobenzene derivatives reveals that the main contribution to the first hyperpolarizability comes from the azo bond, but phenyl meso-substituents can enhance it.</p> </div> </div> </div>

scholarly journals Optical Properties and van der Waals-London Dispersion Interactions in Inorganic and Biomolecular Assemblies

2014 ◽  
Vol 1619 ◽  
Author(s):  
Daniel M. Dryden ◽  
Yingfang Ma ◽  
Jacob Schimelman ◽  
Diana Acosta ◽  
Lijia Liu ◽  
...  
Keyword(s):  
Optical Properties ◽  
Spectroscopic Ellipsometry ◽  
Density Functional ◽  
Type I Collagen ◽  
Strong Dependence ◽  
Van Der Waals ◽  
Fundamental Absorption Edge ◽  
Type I ◽  
Dispersion Interactions ◽  
London Dispersion

ABSTRACTThe optical properties and electronic structure of AlPO4, SiO2, Type I collagen, and DNA were examined to gain insight into the van der Waals-London dispersion behavior of these materials. Interband optical properties of AlPO4 and SiO2 were derived from vacuum ultraviolet spectroscopy and spectroscopic ellipsometry, and showed a strong dependence on the crystals’ constituent tetrahedral units, with strong implications for the role of phosphate groups in biological materials. The UV-Vis decadic molar absorption of four DNA oligonucleotides was measured, and showed a strong dependence on composition and stacking sequence. A film of Type I collagen was studied using spectroscopic ellipsometry, and showed a characteristic shoulder in the fundamental absorption edge at 6.05 eV. Ab initio calculations based on density functional theory corroborated the experimental results and provided further insights into the electronic structures, interband transitions and vdW-Ld interaction potentials for these materials.

scholarly journals Including dispersion interactions in the ONETEP program for linear-scaling density functional theory calculations

2008 ◽  
Vol 465 (2103) ◽  
pp. 669-683 ◽  
Author(s):  
Quintin Hill ◽  
Chris-Kriton Skylaris
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Computational Cost ◽  
Density Functional Theory Calculations ◽  
Binding Energies ◽  
Molecular Structures ◽  
Dispersion Interactions ◽  
Biomolecular Systems ◽  
Functional Theory ◽  
High Level

While density functional theory (DFT) allows accurate quantum mechanical simulations from first principles in molecules and solids, commonly used exchange-correlation density functionals provide a very incomplete description of dispersion interactions. One way to include such interactions is to augment the DFT energy expression by damped London energy expressions. Several variants of this have been developed for this task, which we discuss and compare in this paper. We have implemented these schemes in the ONETEP program, which is capable of DFT calculations with computational cost that increases linearly with the number of atoms. We have optimized all the parameters involved in our implementation of the dispersion correction, with the aim of simulating biomolecular systems. Our tests show that in cases where dispersion interactions are important this approach produces binding energies and molecular structures of a quality comparable with high-level wavefunction-based approaches.

scholarly journals Spin-component-scaled and dispersion-corrected second-order Møller-Plesset perturbation theory: A path toward chemical accuracy

2021 ◽  
Author(s):  
Chandler Greenwell ◽  
Jan Rezac ◽  
Gregory Beran
Keyword(s):  
Perturbation Theory ◽  
Density Functional ◽  
Correlation Energy ◽  
Computational Cost ◽  
Second Order ◽  
Spin Component ◽  
Dispersion Interactions ◽  
Reaction Energies ◽  
Moller Plesset ◽  
Plesset Perturbation Theory

Second-order Møller-Plesset perturbation theory (MP2) provides a valuable alternative to density functional theory for modeing problems in organic and biological chemistry. However, MP2 suffers from known lim- itations in the description of van der Waals dispersion interactions and reaction thermochemistry. Here, a spin-component-scaled, dispersion-corrected MP2 model (SCS-MP2D) is proposed that addresses these weaknesses. The dispersion correction, which is based on Grimme’s D3 formalism, replaces the uncoupled Hartree-Fock dispersion inherent in MP2 with a more robust coupled Kohn-Sham treatment. The spin- component scaling of the residual MP2 correlation energy then reduces the remaining errors in the model. This two-part correction strategy solves the problem found in earlier spin-component-scaled MP2 models where completely different spin-scaling parameters were needed for describing reaction energies versus in- termolecular interactions. Results on 18 benchmark data sets and two challenging potential energy curves demonstrate that SCS-MP2D considerably improves upon the accuracy of MP2 for intermolecular interac- tions, conformational energies, and reaction energies. Its accuracy and computational cost are competitive with state-of-the-art density functionals such as DSD-BLYP-D3(BJ), revDSD-PBEP86-D3(BJ), ωB97X-V, and ωB97M-V for systems with ∼100 atoms.

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