Performance of Density Functionals for Activation Energies of Zr-Mediated Reactions

Coupled cluster CCSD­(T) calculations with core–valence correlation and complete basis set (CBS) limit extrapolation are used to benchmark the performance of commonly used density functionals in computing energy barriers for Zr-mediated reactions involving zirconocene species. These reactions include (a) insertions of the Zr–H bond of Cp₂Zr­(H)Cl into CC, CC, and CO bonds and (b) C–H activations by ZrN bond in Cp₂ZrNH. The best performing functionals are M06-L, M06, and M06-2X in the M06 series, all having mean unsigned deviations (MUD) less than 2 kcal/mol. The worst performing functional is OLYP, with a distinctly large MUD of more than 10 kcal/mol. Considering also the trends in barrier heights and the systematic barrier height deviation, our best recommended functional is M06-2X. In this work, DFT empirical dispersion correction (DFT-D3) is found to improve the performance of barrier height values for most functionals (especially of OLYP and B3LYP). With DFT empirical dispersion correction, we also recommend M06-2X for reaction barrier calculations of Zr-mediated reactions

Comparative Assessment of DFT Performances in Ru- and Rh-Promoted σ‑Bond Activations

In this work, the performances of 19 density functional theory (DFT) methods are calibrated comparatively on Ru- and Rh-promoted σ-bond (C–H, O–H, and H–H) activations. DFT calibration reference is generated from explicitly correlated coupled cluster CCSD­(T)-F12 calculations, and the 4s4p core–valence correlation effect of the two 4d platinum group transition metals is also included. Generally, the errors of DFT methods for calculating energetics of Ru-/Rh-mediated reactions appear to correlate more with the magnitude of energetics itself than other factors such as metal identity. For activation energy calculations, the best performing functionals for both Ru and Rh systems are MN12SX < CAM-B3LYP < M06-L < MN12L < M06 < ωB97X < B3LYP < LC-ωPBE (in the order of increasing mean unsigned deviations, MUDs, of less than 2 kcal/mol). For reaction energy calculations, best functionals with MUDs less than 2 kcal/mol are PBE0 < CAM-B3LYP ≈ N12SX. The effect of the DFT empirical dispersion correction on the performance of the DFT methods is beneficial for most density functionals tested in this work, reducing their MUDs to different extents. After including empirical dispersion correction, ωB97XD, B3LYP-D3, and CAM-B3LYP-D3 (PBE0-D3, B3LYP-D3, and ωB97XD) are the three best performing DFs for activation energy (reaction energy) calculations, from which B3LYP-D3 and ωB97XD can notably be recommended uniformly for both the reaction energy and reaction barrier calculations. The good performance of B3LYP-D3 in quantitative description of the energetic trends further adds value to B3LYP-D3 and singles this functional out as a reasonable choice in the Ru/Rh-promoted σ-bond activation processes

The NPCR values for encrypting Lena image.

<p>The NPCR values for encrypting Lena image.</p

Cipher image with the wrong key and decrypted images.

<p>(a) shows the cipher image with the value of <i>m</i> changed to 15.000000000000001. (b) is the corresponding decrypted image. (c) is the decrypted image with the value of scrambling key 5001 instead of 5000, which has obvious differences from the Lena image in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0084655#pone-0084655-g009" target="_blank">Figure 9</a>. (d) is the decrypted image with the diffusion key <i>p_i+</i>₁ changed from 42 to 41 and the value of <i>q_i-</i>₁ remains 100.</p

Plain image.

<p>The plain image has the same size with the <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0084655#pone-0084655-g006" target="_blank">Figure 6</a>.</p

Partial image.

<p>This image is partial enlarged one from the <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0084655#pone-0084655-g004" target="_blank">Figure 4</a>, and the enlarged area is −0.466866–0.426705 of X-axis, and −0.603235–0.563074 of Y-axis.</p

Effects of IL-17 on proliferation, apoptosis, adhesion, migration and EMT properties of MM1S cells.

<p>(A) IL-17 induced cell proliferation was analyzed by WST-8 assays (left) and Trypan Blue exclusion viable cell assay (right). (B) IL-17 inhibited cell apoptosis determined by Annexin-V binding assay (top), Ki-67 staining (middle), and TUNEL assay (bottom). (C) Canonical histogram of apoptotic rate characterized by Annexin-FITC positive cells was shown. (D) IL-17 decreased cell adhesion to fibronectin and collagen I. (E) IL-17 increased cell migration. (F) IL-17 induced EMT and Rac1 expression of cells. Epithelial marker E-cadherin, mesenchymal marker Vimentin, EMT transcription factors Snail and Slug, and Rac1 expression were detected by western blot analysis. Note all the effects induced by IL-17 were in a dose-dependent manner. (**P<0.01, *P<0.05, Figure is representative of 3 experiments with similar results.).</p

Cipher image.

<p>The encryption image is obtained through the scrambling process and the diffusion process.</p

Hilbert scrambling pseudocode.

<p>Hilbert scrambling pseudocode.</p

Different ratio between Lena image and encrypting Lena image with a certain key changed.

<p>Different ratio between Lena image and encrypting Lena image with a certain key changed.</p