Angular momenta and eigenvectors of the weakly coupled T ⊗ t Jahn‐Teller system

The eigenvalues of the weakly coupled T ? t Jahn‐Teller problem are known for several decades, and the same holds also true for the eigenstates. These, however, are only given in the traditional position representation, which proves inconvenient if one attempts to extend the weak‐coupling treatment into the region of stronger coupling. Here the solution of the T ? t eigenvalue problem at weak coupling is derived in terms of creation and annihilation operators. This reformulation of the problem is nontrivial, since the algebraic form of the oscillator eigenvectors, being simultaneous angular‐momentum eigenstates, has been worked out only recently and is probably still widely unknown. The electronic and oscillator eigenstates are then coupled to form eigenvectors of the total angular momentum. Finally, in preparation for an extension of the weak‐coupling treatment, the action of the boson creation and annihilation operators on the oscillator eigenvectors is calculated, thus completing the algebraic approach to the weakly coupled T ? t system.     

Dynamic stability of carbonyl ylides

The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.     

E ⊗ ϵ Jahn–Teller anharmonic coupling for an octahedral system

The coupling between doubly degenerate electronic states and doubly degenerate vibrations is analyzed for an octahedral system on the basis of the introduction of an anharmonic Morse potential for the vibronic part. The vibrations are described by anharmonic coherent states and their linear coupling with the electronic states is considered. The matrix elements of the vibronic interaction are built and the energy levels corresponding to the interaction Hamiltonian derived. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Cu(II) in liquid ammonia: an approach by hybrid quantum-mechanical/molecular-mechanical molecular dynamics simulation.

To investigate the solvation structure of the Cu(II) ion in liquid ammonia, ab initio quantum-mechanical/molecular-mechanical (QM/MM) molecular dynamics (MD) simulations were carried out at Hartree Fock (HF) and hybrid density functional theory (B3 LYP) levels. A sixfold-coordinated species was found to be predominant in the HF case whereas five- and sixfold-coordinated complexes were obtained in a ratio 2:1 from the B3 LYP simulation. In contrast to hydrated Cu(II), which exhibits a typical Jahn-Teller distortion, the geometrical arrangement of ligand molecules in the case of ammonia can be described as a [2 + 4] ([2 + 3]) configuration with 4 (3) elongated copper-nitrogen bonds. First shell solvent exchange reactions at picosecond rate took place in both HF and B3 LYP simulations, again in contrast to the more stable sixfold-coordinated hydrate. NH3 ligands apparently lead to strongly accelerated dynamics of the Cu(II) solvate due to the "inverse" [2 + 4] structure with its larger number of elongated copper-ligand bonds. Several dynamical properties, such as mean ligand residence times or ion-ligand stretching frequencies, prove the high lability of the solvated complex.     

Quantum‐Chemical and Electrochemical Investigation of the Electrochemical Windows of Halogenated Carborate Anions

The range of electrochemical stability of a series of weakly coordinating halogenated (Hal=F, Cl, Br, I) 1‐carba‐closo‐dodecaborate anions, [1‐R‐CB₁₁X₅Y₆]^? (R=H, Me; X=H, Hal, Me; Y=Hal), has been established by using quantum chemical calculations and electrochemical methods. The structures of the neutral and dianionic radicals, as well as the anions, have been optimized by using DFT calculations at the PBE0/def2‐TZVPP level. The calculated structures are in good agreement with existing experimental data and with previous calculations. Their gas‐phase ionization energies and electron affinities were calculated based on their optimized structures and were compared with experimental (cyclic and square‐wave) voltammetry data. Electrochemical oxidation was performed in MeCN at room temperature and in liquid sulfur dioxide at lower temperatures. All of the anions show a very high resistance to the onset of oxidation (2.15–2.85 V versus Fc^0/+), with only a minor dependence of the oxidation potential on the different halogen substituents. In contrast, the reduction potentials in MeCN are strongly substituent dependent (?1.93 to ?3.32 V versus Fc^0/+). The calculated ionization energies and electron affinities correlate well with the experimental redox potentials, which provide important verification of the thermodynamic validity of the mostly irreversible redox processes that are observed for this series. The large electrochemical windows that are afforded by these anions indicate their suitability for electrochemical applications, for example, as supporting electrolytes.     

High Compression‐Induced Conductivity in a Layered Cu–Br Perovskite

We show that the onset pressure for appreciable conductivity in layered copper‐halide perovskites can decrease by ca. 50 GPa upon replacement of Cl with Br. Layered Cu–Cl perovskites require pressures >50 GPa to show a conductivity of 10^?4 S cm^?1, whereas here a Cu–Br congener, (EA)₂CuBr₄ (EA=ethylammonium), exhibits conductivity as high as 2×10^?3 S cm^?1 at only 2.6 GPa, and 0.17 S cm^?1 at 59 GPa. Substitution of higher‐energy Br 4p for Cl 3p orbitals lowers the charge‐transfer band gap of the perovskite by 0.9 eV. This 1.7 eV band gap decreases to 0.3 eV at 65 GPa. High‐pressure X‐ray diffraction, optical absorption, and transport measurements, and density functional theory calculations allow us to track compression‐induced structural and electronic changes. The notable enhancement of the Br perovskite's electronic response to pressure may be attributed to more diffuse Br valence orbitals relative to Cl orbitals. This work brings the compression‐induced conductivity of Cu‐halide perovskites to more technologically accessible pressures.     

Jahn–Teller coupled charge density wave in a double exchange system

In a two orbital model, we formulate Jahn–Teller coupled charge density wave in one electron per lattice site limit. Softening of Jahn–Teller phonons corresponding to distortion modes Q₂ or Q₃ associated with perfect nesting of Fermi surface leads to this instability at low temperature. The gap equation for charge density wave state and its dependences on electron–lattice coupling are calculated explicitly when any one of the Jahn–Teller modes is excited cooperatively. We find that the Q₂ distortion mode yields lowest free energy. Effect of electron–lattice interaction on collective mode, such as amplitude mode, is more pronounced when the excited mode is Q₂.     

The effect of the B-site size on the structural,magnetic and electrical properties of La0.7Ca0.3MnO3−δ compounds

The perovskite-type ceramic La_0.7Ca_0.3MnO_3−δ was prepared by the solid-state reaction with 0.00?δ?0.15. X-ray diffraction, electrical and magnetic measurements were performed to examine the effect of the B-site size on the properties of these materials. We have found that the structure is orthorhombic for 0.00?δ?0.075 and becomes rhombohedral for 0.10?δ?0.15. The measurements of the magnetization as a function of the temperature, M(T), shows a ferromagnetic-paramagnetic transition at the Curie temperature T_C for δ=0.00. When increasing δ, these curves report the presence of two types of transitions. The first one is from the ferromagnetic to the antiferromagnetic state, indicating the existence of a charge-ordering state (T_CO). The second antiferromagnetic-paramagnetic transition occurs at the Neel temperature T_N. The temperature dependence of the resistivity ρ(T), indicates a metallic behaviour at low temperature (T<T_p) and a semiconductor behaviour at high temperature (T>T_p) for δ=0.00. For 0.05?δ?0.10, the ρ(T) curves shows a semiconductor behaviour revealing the disappearance of the metallic state which reappear at low temperature for δ=0.125 and 0.150.