Search results for "Antibonding molecular orbital"
showing 10 items of 17 documents
High pressure theoretical and experimental analysis of the bandgap of BaMoO4, PbMoO4, and CdMoO4
2019
We have investigated the origin of the bandgap of BaMoO4, PbMoO4, and CdMoO4 crystals on the basis of optical absorption spectroscopy experiments and ab initio electronic band structure, density of states, and electronic localization function calculations under high pressure. Our study provides an accurate determination of the bandgaps Eg and their pressure derivatives d E g / dP for BaMoO4 (4.43 eV, −4.4 meV/GPa), PbMoO4 (3.45 eV, −53.8 meV/GPa), and CdMoO4 (3.71 eV, −3.3 meV/GPa). The absorption edges were fitted with the Urbach exponential model which we demonstrate to be the most appropriate for thick crystals with direct bandgaps. So far, the narrowing of the bandgap of distinct PbMoO4…
On the Road to MM′X Polymers: Redox Properties of Heterometallic Ni···Pt Paddlewheel Complexes
2014
On the quest of heterometallic mixed-valence MM'X chains, we have prepared two stable discrete bimetallic compounds: the reduced (PPN)[ClNi(μ-OSCPh)4Pt] (PPN = bis(triphenylphosphine)iminium; OSCPh = benzothiocarboxylato) and the oxidized [(H2O)Ni(μ-OSCPh)4PtCl] species. The role of the aqua and chlorido axial ligands is crucial to facilitate oxidation of the {Ni(μ-OSCPh)4Pt} core. Experimental and theoretical analyses indicate that a NiPt-Cl/Cl-NiPt isomerization process occurs in the oxidized species. The electronic structure of the reduced system shows two unpaired electrons, one located in a d(x(2)-y(2)) orbital of the Ni(II) ion and a second in the antibonding d(z(2)-dz(2)) combination…
A P-chirogenic β-aminophosphine synthesis by diastereoselective reaction of the α-metallated PAMP–borane complex with benzaldimine
2004
International audience; The diastereoselective synthesis of a P-chirogenic β-aminophosphine ligand with carbon–carbon bond formation of the ethano bridge in a 3:1 ratio via reaction of an α-metallated P-chirogenic phosphine borane with a benzaldimine is described. The diastereoselectivity is attributed to a transition state where the lithium cation chelates the phosphine borane carbanion and the nitrogen of the imine and the attack of the C@N occurs on the face opposite to the P–B bond, due to its interaction with the antibonding P–B bond. The major diastereoisomeric β-aminophosphine borane was then separated and decomplexed into the corresponding β-aminophosphine under neutral conditions a…
Colossal Density-Driven Resistance Response in the Negative Charge Transfer Insulator MnS2
2021
A reversible density driven insulator to metal to insulator transition in high-spin MnS_{2} is experimentally observed, leading with a colossal electrical resistance drop of 10^{8} Ω by 12 GPa. Density functional theory simulations reveal the metallization to be unexpectedly driven by previously unoccupied S_{2}^{2-} σ_{3p}^{*} antibonding states crossing the Fermi level. This is a unique variant of the charge transfer insulator to metal transition for negative charge transfer insulators having anions with an unsaturated valence. By 36 GPa the emergence of the low-spin insulating arsenopyrite (P2_{1}/c) is confirmed, and the bulk metallicity is broken with the system returning to an insula…
Ground state and electronic spectrum of Cu(ii) and Cu(iii) complexes of N,N′-1,2-phenylenebis-2-mercaptoacetamide
2009
The electronic structure and the UV-vis spectrum of reduced and oxidized model systems of the N,N'-1,2-phenylenebis(2-mercapto-2-methylpropionamide) copper complex have been studied using a multiconfigurational quantum chemical method (CASSCF/CASPT2). The bonds between Cu and the two sulfur ligand atoms have a large covalent character in the oxidized Cu(III) form. As a result of the increased covalency, the effective charge on the Cu atom is actually smaller in the oxidized form. The electronic spectrum for both oxidation states of the complex is in agreement with the experiment for excitation energies and intensities showing that the theoretical description of the electronic structure is e…
Spin Transitions in Iron(II) Complexes
1996
Iron(II) has the 3d6 outer electronic configuration and hence its octahedral complexes may be either high-spin or low-spin. The high-spin configuration, t 2g 4 e g 2 , is adopted when relatively weak-field ligands are coordinated while the low-spin, t 2g 6 e g 0 , is obtained when strong-field ligands are involved. In Oh symmetry the ground states are 5T2g and lA1g, for the high-spin and low-spin configurations, respectively. While in most iron(II) six-coordinate complexes the symmetry is lower than Oh, these designations are generally adopted in the following sections for convenience. [Fe(H2O)6]2+ and [Fe(en)3]2+ (en = ethylenediamine) are typical examples of high-spin complexes, while [Fe…
Two- and three-state conical intersections in the electron capture dissociation of disulfides: The importance of multireference calculations
2011
The SS bond cleavage produced upon electron attachment to disulfides was generally assumed to be an adiabatic process because the added electron occupies the σ*(SS) antibonding orbital. This is clearly the case in the parent HSSH compound, but not necessarily in XSSX′ derivatives, where the substituents X and X′ are different. Through the use of MS-CASPT2 calculations, we have shown that the dissociation of the SS two-center-three-electron bond in these asymmetric XSSX′ compounds requires the interaction of at least two states, in order to localize the extra electron in one of the fragments upon dissociation. This is actually the case for the CH3SSNH2 derivative, where the most favorable di…
Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation
2016
Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot elect…
Understanding the microscopic processes that govern the charge-induced deformation of carbon nanotubes
2009
While carbon nanotubes have technological potential as actuators, the underlying actuation mechanisms remain poorly understood. We calculate charge-induced stresses and strains for electrochemical actuation of carbon nanotubes with different chiralities and defects, using density-functional theory and various tight-binding models. For a given deformation mode the concept of bonding and antibonding orbitals can be redefined depending on the sign of a differential band-structure stress. We use this theoretical framework to analyze orbital contributions to the actuation. These show charge asymmetric behavior which is due to next-nearest-neighbor hopping while Coulombic contributions account fo…
Synthesis and characterization of copper intercalated ZrTe3
1997
Abstract Electrochemical copper intercalation in ZrTe3 yields the new metallic ternary phase CuxZrTe3 with a maximum stoichiometry of x = 1.9. The charge is balanced by filling the σ∗ antibonding Te p bands, as monitored by XANES spectroscopy. The reaction is accompanied by an increase in the a lattice dimension of 9%. This observation is explained by theoretical calculations.