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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Do Double-Hybrid Exchange-Correlation Functionals Provide Accurate Chemical Shifts? A Benchmark Assessment for Proton NMR

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Author(s):
de Oliveira, Marcelo T. [1, 2] ; Alves, Julia M. A. [1] ; Braga, Ataualpa A. C. [3] ; Wilson, David J. D. [2] ; Barboza, Cristina A. [4]
Total Authors: 5
Affiliation:
[1] Univ Sao Paulo, Chem Inst Sao Carlos, BR-13566590 Sao Carlos, SP - Brazil
[2] La Trobe Univ, La Trobe Inst Mol Sci, Dept Chem & Phys, Melbourne, Vic 3086 - Australia
[3] Univ Sao Paulo, Inst Quim, BR-05508000 Sao Paulo - Brazil
[4] Polish Acad Sci, Inst Phys, PL-02668 Warsaw - Poland
Total Affiliations: 4
Document type: Journal article
Source: JOURNAL OF CHEMICAL THEORY AND COMPUTATION; v. 17, n. 11, p. 6876-6885, NOV 9 2021.
Web of Science Citations: 0
Abstract

A benchmark density functional theory (DFT) study of H-1 NMR chemical shifts for data sets comprising 200 chemical shifts, including complex natural products, has been carried out to assess the performance of DFT methods. Two new benchmark data sets, NMRH33 and NMRH148, have been established. The meta-GGA revTPSS performs remarkably well against the NMRH33 benchmark set (mean absolute deviation (MAD), 0.10 ppm; maximum deviation (max), 0.26 ppm) with the smallest MAD of all evaluated functionals. The best-performing double-hybrid density functional (DHDF), revDSD-BLYP (MAD, 0.16 ppm; max, 0.35 ppm), performs similarly to hybrid-GGA methods (e.g., mPW1PW91/6-311G(d) (MAD, 0.15 ppm; max, 0.36 ppm)), but at a considerably higher computational cost. The results indicate that currently available double-hybrid DFT methods offer no benefit over GGA (including hybrid and meta) functionals in the calculation of H-1 NMR chemical shifts. (AU)

FAPESP's process: 13/07375-0 - CeMEAI - Center for Mathematical Sciences Applied to Industry
Grantee:Francisco Louzada Neto
Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
FAPESP's process: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes
Grantee:Carlos Roque Duarte Correia
Support Opportunities: Research Projects - Thematic Grants
FAPESP's process: 15/01491-3 - Theoretical study of cross-coupling reactions: homogeneous and heterogeneous catalysis
Grantee:Ataualpa Albert Carmo Braga
Support Opportunities: Regular Research Grants
FAPESP's process: 13/07600-3 - CIBFar - Center for Innovation in Biodiversity and Drug Discovery
Grantee:Glaucius Oliva
Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC