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XYG3 Results for Some Selected Applications

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A New-Generation Density Functional

Part of the book series: SpringerBriefs in Molecular Science ((BRIEFSMOLECULAR))

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Abstract

In this chapter, some selected applications of the XYG3 functionals are described. In Sect. 4.1, a set of gas-phase reactions relevant to the Fischer–Tropsch synthesis has been constructed. With this set, we have tested the validity of the widely used PBE and B3LYP functionals, as well as XYG3. As gas-phase reactions and the corresponding surface reactions are related through the Born–Haber cycle, we argued that computational catalysis on surfaces will be less meaningful if gas-phase behaviors cannot first be suitably determined. In Sect. 4.2, we predict the heat formation of 5-chloromethylfurfural (CMF), which has been proposed as a central intermediate in the conversion of carbohydrate-based material into useful organic commodities. Using XYG3, the conversion from CMF to 5-Hydroxymethylfurfural (HMF) and levulinic acid (LA) in water, and that to biofuels 5-ethoxymethyl furfural (EMF) or ethyllevulinate (EL) in alcohol have been studied. New reaction mechanisms have been proposed, which complement the well-recognized Horvat’s mechanisms. In Sect. 4.3, we have reported the XYG3 results on the processes for d-glucose pyrolysis to acrolein. It has been shown that the most feasible reaction pathway starts from an isomerization from d-glucose to d-fructose, which then undergoes a cyclic Grob fragmentation, followed by a concerted electrocyclic dehydration to yield acrolein. This study provides the first mechanism based on theory that can account for the known experimental results. In Sect. 4.4, a non-fitting protein–ligand interaction scoring function has been introduced and applied to the screening of kinase inhibitors. A good correlation has been found between the calculated scores and the experimental inhibitor efficacies with the square of correlation coefficient R 2 of 0.88 when XYG3 is used to calculate the relative binding enthalpies in the gas phase. Such a good performance can only be achieved after proper treatment of the solvation effects, as well as the entropic effects on the relative binding affinities. This represents the first high-level theory based non-fitting scoring function.

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  1. Department of Chemistry, Fudan University, Shanghai, People’s Republic of China

    Igor Ying Zhang & Xin Xu

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Zhang, I.Y., Xu, X. (2014). XYG3 Results for Some Selected Applications. In: A New-Generation Density Functional. SpringerBriefs in Molecular Science. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-40421-4_4

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