Comprehensive Benchmark of Association (Free) Energies of Realistic Host–Guest Complexes

Sure, Rebecca; Grimme, Stefan

doi:10.1021/acs.jctc.5b00296

Cited by 215 publications

(376 citation statements)

References 136 publications

Supporting

Mentioning

361

Contrasting

Order By: Relevance

“…The S30L test set consists of 30 "real" supramolecular host-guest complexes. 138 The reference energies of the S30L complexes vary between 20 kcal/mol and 150 kcal/mol. Because multiple hydrogen bonds are present and nine systems are charged, the S30L benchmark is challenging for any electronic structure method.…”

Section: General Interaction and Reaction Energiesmentioning

confidence: 99%

Consistent structures and interactions by density functional theory with small atomic orbital basis sets

Grimme

Brandenburg

Bannwarth

et al. 2015

The Journal of Chemical Physics

Self Cite

771

728

View full text Add to dashboard Cite

A density functional theory (DFT) based composite electronic structure approach is proposed to efficiently compute structures and interaction energies in large chemical systems. It is based on the well-known and numerically robust Perdew-Burke-Ernzerhoff (PBE) generalized-gradient-approximation in a modified global hybrid functional with a relatively large amount of non-local Fock-exchange. The orbitals are expanded in Ahlrichs-type valence-double zeta atomic orbital (AO) Gaussian basis sets, which are available for many elements. In order to correct for the basis set superposition error (BSSE) and to account for the important long-range London dispersion effects, our well-established atom-pairwise potentials are used. In the design of the new method, particular attention has been paid to an accurate description of structural parameters in various covalent and non-covalent bonding situations as well as in periodic systems. Together with the recently proposed three-fold corrected (3c) Hartree-Fock method, the new composite scheme (termed PBEh-3c) represents the next member in a hierarchy of "low-cost" electronic structure approaches. They are mainly free of BSSE and account for most interactions in a physically sound and asymptotically correct manner. PBEh-3c yields good results for thermochemical properties in the huge GMTKN30 energy database. Furthermore, the method shows excellent performance for non-covalent interaction energies in small and large complexes. For evaluating its performance on equilibrium structures, a new compilation of standard test sets is suggested. These consist of small (light) molecules, partially flexible, medium-sized organic molecules, molecules comprising heavy main group elements, larger systems with long bonds, 3d-transition metal systems, non-covalently bound complexes (S22 and S66×8 sets), and peptide conformations. For these sets, overall deviations from accurate reference data are smaller than for various other tested DFT methods and reach that of triple-zeta AO basis set second-order perturbation theory (MP2/TZ) level at a tiny fraction of computational effort. Periodic calculations conducted for molecular crystals to test structures (including cell volumes) and sublimation enthalpies indicate very good accuracy competitive to computationally more involved plane-wave based calculations. PBEh-3c can be applied routinely to several hundreds of atoms on a single processor and it is suggested as a robust "high-speed" computational tool in theoretical chemistry and physics.

show abstract

Section: General Interaction and Reaction Energiesmentioning

confidence: 99%

Consistent structures and interactions by density functional theory with small atomic orbital basis sets

Grimme

Brandenburg

Bannwarth

et al. 2015

The Journal of Chemical Physics

Self Cite

771

728

View full text Add to dashboard Cite

show abstract

“…50 Since the contribution from London dispersion forces is strictly attractive in the ground state, the magnitude of the interaction grows with the system size and can even increase to the level of covalent bonds in magnitude. 53 In wavefunction based EDAs, the terms "dispersion" and "correlation" are often used interchangeably, while in a majority of DFT based EDAs "dispersion" is defined directly from the chosen correction that is applied to the chosen density functional. Proceeding in this manner is problematic primarily Box 2.…”

Section: B Trouble With London Dispersionmentioning

confidence: 99%

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

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

110

102

View full text Add to dashboard Cite

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

show abstract

“…As an approximation, the additional imaginary frequencies were inverted into frequencies with positive values in the G calculations of these TS1 as seen previously. [23] [b] n.d. = not determined.…”

Section: P1(a) P1(b)mentioning

confidence: 99%

Optimizing the Accuracy and Computational Cost in Theoretical Squaramide Catalysis: The Henry Reaction

Alegre‐Requena

Marqués‐López

Herrera

2017

Chemistry A European J

View full text Add to dashboard Cite

This study represents the first example where the accuracy of different combinations of density functional theory (DFT) methods and basis sets has been compared in squaramide catalysis. After an optimization process of the precision obtained and the computational time required in the computational calculations, highly precise results were achieved compared to the experimental outcomes while using the least amount of time as possible. Here, we have explored computationally and experimentally the mechanism of squaramide-catalyzed Henry reaction. This is a complex reaction of about 100 atoms and a great number of diverse non-covalent interactions. Moreover, this research is one of the scarce examples where the organocatalyst acts in a trifunctional manner and is the first investigation in which a trifunctional squaramide catalyst has been employed. Functional ωB97X-D showed the best results when used with different versions of the 6-311 basis sets, leading to highly accurate calculations of the outcomes of the Henry reaction using nine aldehydes with different structural characteristics. Furthermore, in these relatively large systems, the use of a split-valence triple-zeta basis set saves a large amount of time compared to using larger basis sets that are sometimes employed in organocatalytic studies, such as the TZV and Def2TZV basis set families.

show abstract

Comprehensive Benchmark of Association (Free) Energies of Realistic Host–Guest Complexes

Cited by 215 publications

References 136 publications

Consistent structures and interactions by density functional theory with small atomic orbital basis sets

Consistent structures and interactions by density functional theory with small atomic orbital basis sets

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

Optimizing the Accuracy and Computational Cost in Theoretical Squaramide Catalysis: The Henry Reaction

Contact Info

Product

Resources

About