We present two new hybrid meta exchange- correlation functionals, called M06 and M06-2X. The M06 functional is parametrized including both transition metals and nonmetals, whereas the M06-2X functional is a high-nonlocality functional with double the amount of nonlocal exchange (2X), and it is parametrized only for nonmetals.The functionals, along with the previously published M06-L local functional and the M06-HF full-Hartree–Fock functionals, constitute the M06 suite of complementary functionals. We assess these four functionals by comparing their performance to that of 12 other functionals and Hartree–Fock theory for 403 energetic data in 29 diverse databases, including ten databases for thermochemistry, four databases for kinetics, eight databases for noncovalent interactions, three databases for transition metal bonding, one database for metal atom excitation energies, and three databases for molecular excitation energies. We also illustrate the performance of these 17 methods for three databases containing 40 bond lengths and for databases containing 38 vibrational frequencies and 15 vibrational zero point energies. We recommend the M06-2X functional for applications involving main-group thermochemistry, kinetics, noncovalent interactions, and electronic excitation energies to valence and Rydberg states. We recommend the M06 functional for application in organometallic and inorganometallic chemistry and for noncovalent interactions.

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The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

Density functional theory for transition metals and transition metal chemistry

Recent Developments in the Preparation and Chemistry of Metallacycles and Metallacages via Coordination

A study is conducted to demonstrate catalytic dehydrogenation of light alkanes on metals and metal oxides. The study provides a complete overview of the materials used to catalyze this reaction, as dehydrogenation for the production of light olefins has become extremely relevant. Relevant factors, such as the specific nature of the active sites, as well as the effect of support, promoters, and reaction feed on catalyst performance and lifetime, are discussed for each catalytic Material. The study compares different catalysts in terms of the reaction mechanism and deactivation pathways and catalytic performance. The duration of the dehydrogenation step depends on the heat content of the catalyst bed, which decreases rapidly due to the endothermic nature of the reaction. Part of the heat required for the reaction is introduced to the reactors by preheating the reaction feed, additional heat being provided by adjacent reactors that are regenerating the coked catalysts.

Catalytic dehydrogenation of light alkanes on metals and metal oxides.

Shape-controlled metal nanocrystals possess the advantages of specific atomic arrangement on the surface and uniform size, which can act as ideal model catalysts for heterogeneous enantioselective catalytic studies. Nevertheless, capping agents are commonly retained on the surface of the as-synthesized metal nanocrystals, which may hinder the necessary interaction between the substrate and the chiral modifiers coadsorbed on the metal surface for chiral recognition. In this paper, we directly synthesized dendritic or cubic palladium nanocrystals in-situ modified by chiral modifiers such as cinchonidine (CD) or S-proline through a one-pot strategy by replacing the conventional capping agents with the chiral modifiers. The as-prepared CD-modified Pd nanodendrite catalyst already exhibits enantioselectivity in the asymmetric hydrogenation of (E)-α-phenylcinnamic acid without subsequent chiral modification processes. The in-situ S-proline-modified Pd nanocube catalyst shows higher enantioselectivity than nanoc...

Direct Synthesis of in-Situ Chirally Modified Palladium Nanocrystals without Capping Agents and Their Application in Heterogeneous Enantioselective Hydrogenations

Linear regression correction to first principle theoretical calculations - improved descriptors and enlarged training set

Activation of C–C Bonds via σ-Bond Metathesis: Hydroborenium-Catalyzed Hydrogenolysis of Cyclopropanes

The invention discloses a one-step electro-synthesis method of an iron-layered double hydroxide nanosheet array. According to the one-step electro-synthesis method of the iron-layered double hydroxide nanosheet array, the simple and rapid one-step electro-synthesis method is adopted for the first time to prepare different kinds of iron-containing layered double hydroxide nanosheet arrays on multiple kinds of conductive substrates, and a universal method is provided for easy and rapid preparation of the iron-layered double hydroxides; and the size and the density of layered double hydroxide nanosheets are well controlled through adjustment of the electro-synthesis time, and the best performance of the layered double hydroxide nanosheets is achieved. By the adoption of the one-step electro-synthesis method of the iron-layered double hydroxide nanosheet array, a brand-new universal method for preparing the iron-layered double hydroxide nanosheet array is provided, the application fields of the layered double hydroxide type materials are widened, the layered double hydroxide type material of the nanosheet array structure has quite broad application prospect in the aspects such as the electrolysis oxygen evolution reaction (OER), the supercapacitor electrode material (SCs), the lithium ion battery electrode material and biological sensing.

Zhen Hua Li

Papers

Direct Synthesis of in-Situ Chirally Modified Palladium Nanocrystals without Capping Agents and Their Application in Heterogeneous Enantioselective Hydrogenations

Linear regression correction to first principle theoretical calculations - improved descriptors and enlarged training set

Activation of C–C Bonds via σ-Bond Metathesis: Hydroborenium-Catalyzed Hydrogenolysis of Cyclopropanes

One-step electro-synthesis method of iron-layered double hydroxide nanosheet array

Activation of the P–H bond by a frustrated Lewis pair and its application in catalytic Z-selective hydrophosphonylation of terminal ynones