7 research outputs found

    Treating London-Dispersion Effects with the Latest Minnesota Density Functionals: Problems and Possible Solutions

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    It is shown that the latest Minnesota density functionals (SOGGA11, M11-L, N12, MN12-L, SOGGA11-X, M11, N12-SX, and MN12-SX) do not properly describe London-dispersion interactions. Grimme’s DFT-D3 correction can solve this problem partially; however, double-counting of medium-range electron correlation can occur. For the related M06-L functional, the alternative VV10 van der Waals kernel is tested, but it experiences similar double-counting. Most functionals give unphysical dissociation curves for the argon dimer, an indication for method-inherent problems, and further investigation is recommended. These results are further evidence that the London-dispersion problem in density functional theory approximations is unlikely to be solved by mere empirical optimization of functional parameters, unless the functionals contain components that ensure the correct asymptotic long-range behavior. London dispersion is ubiquitous, which is why the reported findings are not only important for theoreticians but also a reminder to the general chemist to carefully consider their choice of method before undertaking computational studies

    How Do DFT-DCP, DFT-NL, and DFT-D3 Compare for the Description of London-Dispersion Effects in Conformers and General Thermochemistry?

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    The dispersion-core-potential corrected B3LYP-DCP method (Torres and DiLabio <i>J. Phys. Chem. Lett.</i> <b>2012</b>, <i>3</i>, 1738) is for the first time thoroughly assessed and compared with the B3LYP-NL (Hujo and Grimme <i>J. Chem. Theory Comput.</i> <b>2011</b>, <i>7</i>, 3866) and B3LYP-D3 (Grimme et al. <i>J. Comput. Chem.</i> <b>2011</b>, <i>32</i>, 1456) methods for a broad range of chemical problems that particularly shed light on intramolecular London-dispersion effects in conformers and general thermochemistry. The analysis is based on a compilation of 473 reference cases, the majority of which are taken from the GMTKN30 database (Goerigk and Grimme <i>J. Chem. Theory Comput.</i> <b>2010</b>, <i>6</i>, 107; <b>2011</b>, <i>7</i>, 291). The results confirm previous findings that B3LYP-DCP indeed predicts very good binding energies for noncovalently bound complexes, particularly with small basis sets. However, problems are identified for the description of intramolecular effects in some conformers and chemical reactions, for which B3LYP-DCP sometimes gives results similar or worse than uncorrected B3LYP. Surprisingly large errors for total atomization energies reveal an unwanted influence of the DCPs on the short-range electronic structure of the investigated systems. However, a recently modified carbon potential for B3LYP-DCP (DiLabio et al. <i>Theor. Chem. Acc.</i> <b>2013</b>, <i>132</i>, 1389) was additionally tested that seems to solve most of those problems and provides improved results. An overall comparison between all tested methods shows that B3LYP-NL is the most robust and accurate approach, closely followed by B3LYP-D3. This is also true when small basis sets of double-ζ quality are applied for which those methods have not been parametrized. However, binding energies of noncovalently bound complexes can be more strongly influenced by basis-set superposition-error effects than for B3LYP-DCP. Finally, it is noted that the DFT-D3 and DFT-NL schemes are readily applicable to a large range of chemical elements and they are therefore particularly recommended for more general applications

    Time-Dependent Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling

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    For the first time, we combine time-dependent double-hybrid density functional approximations (TD-DHDFAs) for the calculation of electronic excitation energies with the concepts of spin-component and spin-opposite scaling (SCS/SOS) of electron-pair contributions to their nonlocal correlation components. Different flavors of this idea, ranging from standard SCS parameters to fully fitted parameter sets, are presented and tested on six different parent DHDFAs. For cross-validation, we assess those methods on three benchmark sets that cover small- to medium-sized chromophores (up to 78 atoms) and different excitation types. For this purpose, we also introduce new CC3 reference values for the popular Gordon benchmark set that we recommend using in future studies. Our results confirm that already the (unscaled) parent TD-DHDFAs are accurate and outperform some wave function methods. Further introduction of SCS/SOS eliminates extreme outliers, reduces deviation spans from reference values by up to 0.5 eV, aligns the performance of the Tamm-Dancoff approximation (TDA) to that of full TD calculations, and also enables a more balanced description of different excitation types. The best-performing TD-based methods in our cross validation have mean absolute deviations as low as 0.14 eV compared to the time- and resource-intensive CC3 approach. A very important finding is that we also obtained SOS variants with excellent performance, contrary to wave function based methods. This opens a future pathway to highly efficient methods for the optimization of excited-state geometries, particularly when paired with computing strategies such as the Laplace transform. We recommend our SCS- and SOS-based variants for further testing and subsequent applications

    Efficient Methods for the Quantum Chemical Treatment of Protein Structures: The Effects of London-Dispersion and Basis-Set Incompleteness on Peptide and Water-Cluster Geometries

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    We demonstrate how quantum chemical Hartree–Fock (HF) or density functional theory (DFT) optimizations with small basis sets of peptide and water cluster structures are decisively improved if London-dispersion effects, the basis-set-superposition error (BSSE), and other basis-set incompleteness errors are addressed. We concentrate on three empirical corrections to these problems advanced by Grimme and co-workers that lead to computational strategies that are both accurate and efficient. Our analysis encompasses a reoptimized version of Hobza’s P26 set of tripeptide structures, a new test set of conformers of cysteine dimers, and isomers of the water hexamer. These systems reflect features commonly found in protein crystal structures. In all cases, we recommend Grimme’s DFT-D3 correction for London-dispersion. We recommend usage of large basis sets such as cc-pVTZ whenever possible to reduce any BSSE effects and, if this is not possible, to use Grimme’s gCP correction to account for BSSE when small basis sets are used. We demonstrate that S–S and C–S bond lengths are very prone to basis-set incompleteness and that polarization functions should always be used on S atoms. At the double-ζ level, the PW6B95-D3-gCP DFT method combined with the SVP and 6-31G* basis sets yields accurate results. Alternatively, the HF-D3-gCP/SV method is recommended, with inclusion of polarization functions for S atoms only. Minimal basis sets offer an intriguing route to highly efficient calculations, but due to significant basis-set incompleteness effects, calculated bond lengths are seriously overestimated, making applications to large proteins very difficult, but we show that Grimme’s newest HF-3c correction overcomes this problem and so makes this computational strategy very attractive. Our results provide a useful guideline for future applications to the optimization, quantum refinement, and dynamics of large proteins

    Why the Standard B3LYP/6-31G* Model Chemistry Should Not Be Used in DFT Calculations of Molecular Thermochemistry: Understanding and Correcting the Problem

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    We analyze the error compensations that are responsible for the relatively good performance of the popular B3LYP/6-31G* model chemistry for molecular thermochemistry. We present the B3LYP-gCP-D3/6-31G* scheme, which corrects for missing London dispersion and basis set superposition error (BSSE) in a physically sound manner. Benchmark results for the general main group thermochemistry, kinetics, and noncovalent interactions set (GMTKN30) are presented. A detailed look is cast on organic reactions of several arenes with C<sub>60</sub>, Diels–Alder reactions, and barriers to [4 + 3] cycloadditions. We demonstrate the practical advantages of the new B3LYP-gCP-D3/6-31G* scheme and show its higher robustness over standard B3LYP/6-31G*. B3LYP-gCP-D3/6-31G* is meant to fully substitute standard B3LYP/6-31G* calculations in the same black-box sense at essentially no increase in computational cost. The energy corrections are made available by a Web service (http://www.thch.uni-bonn.de/tc/gcpd3) and by freely available software

    Recommending Hartree–Fock Theory with London-Dispersion and Basis-Set-Superposition Corrections for the Optimization or Quantum Refinement of Protein Structures

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    We demonstrate the importance of properly accounting for London dispersion and basis-set-superposition error (BSSE) in quantum-chemical optimizations of protein structures, factors that are often still neglected in contemporary applications. We optimize a portion of an ensemble of conformationally flexible lysozyme structures obtained from highly accurate X-ray crystallography data that serve as a reliable benchmark. We not only analyze root-mean-square deviations from the experimental Cartesian coordinates, but also, for the first time, demonstrate how London dispersion and BSSE influence crystallographic <i>R</i> factors. Our conclusions parallel recent recommendations for the optimization of small gas-phase peptide structures made by some of the present authors: Hartree–Fock theory extended with Grimme’s recent dispersion and BSSE corrections (HF-D3-gCP) is superior to popular density functional theory (DFT) approaches. Not only are statistical errors on average lower with HF-D3-gCP, but also the convergence behavior is much better. In particular, we show that the BP86/6-31G* approach should not be relied upon as a black-box method, despite its widespread use, as its success is based on an unpredictable cancellation of errors. Using HF-D3-gCP is technically straightforward, and we therefore encourage users of quantum-chemical methods to adopt this approach in future applications

    Visible-Light-Driven “On”/“Off” Photochromism of a Polyoxometalate Diarylethene Coordination Complex

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    Herein we report the first photochromic polyoxometalate (POM)-based diarylethene (DAE) coordination complex, prepared by ligation of two cobalt­(III)-incorporated borotungstates [B<sup>III</sup>W<sup>VI</sup><sub>11</sub>O<sub>39</sub>Co<sup>III</sup>]<sup>6–</sup> with the ditopic pyridyl-containing diarylethene (C<sub>25</sub>H<sub>16</sub>N<sub>2</sub>F<sub>6</sub>S<sub>2</sub>). The solution-state composition, structure, and stability of the assembly were probed using <sup>1</sup>H and <sup>19</sup>F nuclear magnetic resonance spectroscopy (NMR), electrospray ionization quadrupolar time-of-flight mass spectrometry (ESI-QTOF-MS), ultraviolet–visible spectroscopy (UV–vis), and small-angle X-ray scattering (SAXS), revealing that the complex self-organizes to adopt a molecular dumbbell structure due to electrostatic and steric considerations. This conformation is a prerequisite for the photocyclization reaction. The assembly was found to be switchable between two states using visible light due to the perturbation of the DAE electronic structure on coordination to the POM. We present photophysical data, including the reaction quantum efficiency of the molecular switch in both directions measured using a custom-built quantum yield determination setup in addition to fatigue resistance on prolonged irradiation
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