Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids

Tao, Jianmin; Perdew, John P.; Staroverov, Viktor N.; Scuseria, Gustavo E.

doi:10.1103/physrevlett.91.146401

Cited by 6,054 publications

(5,052 citation statements)

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“…24,25 For this purpose, we employed the TPSS functional. 26 We obtained relative energies and harmonic frequencies at both levels of theory. The numerically calculated harmonic frequencies were scaled by a factor of 0.956 for the RI-MP2 calculations, as used in our previous papers.…”

Section: Theoretical Methodsmentioning

confidence: 99%

The Mid-IR Spectra of 9-Ethyl Guanine, Guanosine, and 2-Deoxyguanosine

et al. 2007

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We present the mid-IR (400-1800 cm -1 ) spectra of 9-ethyl guanine, guanosine, and 2-deoxyguanosine measured by IR-UV double-resonance spectroscopy. We compare the recorded mid-IR spectra with the spectra of the most stable structures obtained from RI-MP2 and RI-DFT-D calculations. The results confirm the enol form for all structures and demonstrate the efficacy of a new approach to DFT calculations that includes dispersion interactions.

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Section: Theoretical Methodsmentioning

confidence: 99%

The Mid-IR Spectra of 9-Ethyl Guanine, Guanosine, and 2-Deoxyguanosine

et al. 2007

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“…The calculations employed either the TPSS [46] or BP86 [47,48] functionals. Basis sets of four different sizes were employed, def2-SV(P), TZVP, def2-TZVP, and def2-QZVP' (i.e.…”

Section: Dft-d Calculationsmentioning

confidence: 99%

Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host–guest binding energies

Mikulskis

Cioloboc

Andrejić

et al. 2014

J Comput Aided Mol Des

220

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Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid hostguest binding energies. Link to publication Citation for published version (APA): Mikulskis, P., Cioloboc, D., Andrejić, M., Khare, S., Brorsson, J., Genheden, S., ... Ryde, U. (2014). Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host-guest binding energies. Journal of Computer-Aided Molecular Design, 28(4), 375-400. DOI: 10.1007/s10822-014-9739-x General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal AbstractWe have estimated free energies for the binding of nine cyclic carboxylate guest molecules to the octa-acid host in the SAMPL4 blind-test challenge with four different approaches. First, we used standard free-energy perturbation calculations of relative binding affinities, performed at the molecular-mechanics (MM) level with TIP3P waters, the GAFF force field, and two different sets of charges for the host and the guest, obtained either with the restrained electrostatic potential or AM1-BCC methods. Both charge sets give good and nearly identical results, with a mean absolute deviation (MAD) of 4 kJ/mol and a correlation coefficient (R 2 ) of 0.8 compared to experimental results. Second, we tried to improve these predictions with 28 800 density-functional theory (DFT) calculations for selected snapshots and the non-Boltzmann Bennett acceptance-ratio method, but this led to much worse results, probably because of a too large difference between the MM and DFT potential-energy functions. Third, we tried to calculate absolute affinities using minimised DFT structures. This gave intermediate-quality results with MADs of 5-9 kJ/mol and R 2 = 0.6-0.8, depending on how the structures were obtained. Finally, we tried to improve these results using local coupled-cluster calculations with single and double excitations, and non-iterative perturbative treatment of triple excitations (LCCSD(T0)), employing the polarisable multipole interactions with supermolecular pairs approach. Unfortunately, this only degraded the predictions, probably because a mismatch between the solvation energies obtained at the DFT and LCCSD(T0) levels.Key Words: binding affinities, host-guest, free-energies perturbation, density-functional calculations, CCSD(T), polarisable multipole interactions. 2 IntroductionOne of the largest challenges of computational chemistry is to predict the binding affinity of a small ligand to a larger receptor molecule, e.g. a drug candidate to its receptor prot...

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“…This approach paved the way to the development of more complex approximations such as TPSS, 33 a non-empirical meta-GGA, or the global-hybrid (GH) PBE0 2,3 rooted in the AC model. 25 Starting by the definition of the exchange-correlation contribution, E xc , to the total KS energy defined as:…”

Section: Theorymentioning

confidence: 99%

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

et al. 2016

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ConspectusDensity Functional Theory (DFT) emerged in the last two decades as the most reliable tool the description and prediction of properties of molecular systems and extended materials, coupling in an unprecedented way high accuracy and reasonable computational cost. This success rests also on the development of more and more performing Density Functional Approximations (DFAs).Indeed, the Achilles' heel of DFT is represented by the exchange-correlation contribution to the total energy, which, being unknown, must be approximated. Since the beginning of the '90s, global hybrids (GH) functionals, where an explicit dependence of the exchange-correlation energy on model. In such a way, a whole family of non-empirical functionals, spanning on the highest rungs of the Perdew's quality scale, is now available and competitive with other -more empirical-DFAs. This is a previous version of the article published in Accounts of Chemical Research. 2016Research. , 49(8): 1503Research. -1513Research. . doi:10.1021 2 Discussion of selected cases, ranging from thermochemistry and reactions to weak interactions and excitations energies, not only show the large range of applicability of non-empirical DFAs, but also underline how increasing the number of theoretical constrains parallel with an improvement of the DFA's numerical performances. This fact further consolidates the strong theoretical framework of non-empirical DFAs.Finally, even if non-empirical DH approaches are still computationally expensive, relying on the fact that they can benefit of all technical enhancements developed for speeding-up post-HartreeFock methods, there is a substantial hope for their near future routine application to the description and prediction of complex chemical systems and reactions.

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Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids

Cited by 6,054 publications

References 31 publications

The Mid-IR Spectra of 9-Ethyl Guanine, Guanosine, and 2-Deoxyguanosine

The Mid-IR Spectra of 9-Ethyl Guanine, Guanosine, and 2-Deoxyguanosine

Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host–guest binding energies

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

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