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.

The present invention discloses a method for preparing a multi-ion embedded supercapacitor through adoption of an electrochemistry alkaline activation method. A simple and rapid electrochemistry alkaline activation method is employed to perform activation or deactivation processing of the transition metal hydroxide containing cobalt or nickel to realize the intelligent regulation and control of storage capacity of metal cations through the hydroxide electrode materials, and is applied to an ion embedded supercapacitor. The present invention provides a universal method capable of improving the storage capacity of the ion embedded supercapacitor electrode materials, and the application range of the transition metal hydroxide electrode materials is further widened in the energy storage field.

Method for preparing multi-ion embedded supercapacitor through adoption of electrochemistry alkaline activation method

Here we describe the coordination-driven self-assembly of organometallic half-sandwich iridium(III)- and rhodium(III)-based building blocks with asymmetric ambidentate pyridyl-carboxylate ligands. Despite the potential for obtaining a statistical mixture of multiple products, D 2 symmetric octanuclear cages were formed selectively by taking advantage of the electronic effects emanating from the two types of chelating sites - ( O , O' ) and ( N , N' ) - on the tetranuclear building blocks. The metal sources and the lengths of bridging ligands show influence on the selectivity of the self-assembly. Experimental observations, supported by computational studies, suggest that the D 2 symmetric cages are the thermodynamically favoured products. Overall, the results underline the importance of electronic effects on the selectivity of coordination-driven self-assembly, and demonstrate that asymmetric ambidentate ligands can be used to control the design of discrete supramolecular coordination complexes.

Coordination-Driven Selective Formation of D2 Symmetric Octanuclear Organometallic Cages

Half-sandwich zirconium complex 3 containing tridentate carborane [S,S,O] ligand 2 [(HOC6H2R2-4,6)(CH2)SC(B10H10) C(Ph)2P=S, R=
 t
 Bu] was synthesized by the reaction of CpZrCl3 (Cp= η
 5-C5H5) with sodium salt of ligand 2. Zirconium complex 3 was characterized by elemental and NMR analyses. DFT calculations were also performed on complex 3 to analyze the stereochemistry. The results from DFT calculations indicate that structure S1, in which no sulfur atom bonds to the zirconium atom, exists at the lowest energy level. In the presence of methylaluminoxane (MAO), complex 3 exhibited good catalytic activities for ethylene polymerization and long life-time up to 10 h. Moreover, the complex 3/MAO system displayed excellent catalytic activities toword ethylene copolymerization with 1-hexene or polar olefins.

Ethylene (co-)polymerization by long-lifetime half-sandwich zirconium catalyst bearing a [SSO]-carborane ligand

Matrix metalloproteinase family as molecular biomarkers in oral squamous cell carcinoma

The invention relates to a sensor material which has electrochemical sensing and colorimetric sensing performances at the same time as well as is applied to qualitative and quantitative determination of glucose or hydrogen peroxide. The material comprises hydrotalcite nanosheet arrays containing cobalt and iron, a simple one-step electrosynthesis method is used, and the cobalt-iron hydrotalcite nanosheets vertically grow on a conductive substrate. The sensor material is used as a catalase-like inorganic nano-material which has good color changing responses in colorimetric sensing analyses of glucose and hydrogen peroxide, linear range of the catalase-like glucose biosensor is 0-800[mu]M, and after 4 times of circulation and repeated usage, the sensing performance is kept at 90% or above; the sensor material has good anti-interference performances for ascorbic acid, dopamine, urea, etc.

Zhen Hua Li

Papers

Method for preparing multi-ion embedded supercapacitor through adoption of electrochemistry alkaline activation method

Coordination-Driven Selective Formation of D2 Symmetric Octanuclear Organometallic Cages

Ethylene (co-)polymerization by long-lifetime half-sandwich zirconium catalyst bearing a [SSO]-carborane ligand

Matrix metalloproteinase family as molecular biomarkers in oral squamous cell carcinoma

Sensor material of qualitative and quantitative determination of glucose as well as preparation method thereof