Anion dependent molecular recognition of cations

In DMF-d₇ tetrabenzimidazole cavitands 2 exist as monomeric species and vase-like conformers. Several possible arrangements of the four benzimidazole NHs are indicated by ¹H NMR spectroscopy. The cavitands form 1:1 inclusion complexes with tetraethyl ammonium and phosphonium cations only when strong hydrogen bonding anions like chloride or acetate are present. These complexes are stable on the NMR time scale at 295 K feature a C_2V-symmetrical arrangement of benzimidazole functions. The stability of the C_2V-symmetrical tetramethylammonium acetate complex is independent of the temperature. In contrast, tetramethylammonium and phosphonium chloride complexes exist at 233 K as several isomers. This complicated behavior is, in part, attributed to the hydrogen bonding interactions between the anions and the NH groups of benzimidazole functions.     

An environmental pseudopotential approach to molecular interactions: Implementation in MOLPRO

We present the implementation into the MOLPRO package of a model for the interaction of a central system with its surrounding environment. The properties of a target system enclosed by a noncovalently bound environment or solvent are modeled as those of a system embedded into the effective pseudopotential arising from the exact electrostatic Coulomb potential and the approximated exchange-repulsion potential. For the latter we use the charge-density overlap model, which relates the exchange-repulsion interaction energy between two species with the overlap of their ground-state electron charge densities. The solutions of the modified Hartree-Fock equations for the target system are obtained self-consistently. This way the exchange-induction effects arising from the converged electron-charge density of the embedded system are implicitly included. Inclusion of the correlation effects is provided by the use of post-Hartree-Fock and density-functional techniques available in the MOLPRO package. The computational and conceptual advantages provided by this approach are shown in the calculation of the dipole polarizabilities of halide and chalcogenide anions in different environments.     

Theoretical study of rhodium(I) carbene complexes: the structural versatility of phosphino- compared with aminocarbenes

Density functional calculations are reported for complexes of general formula [(carbene)RhClL(2)] featuring model phosphino- and aminocarbenes. Both the cis and trans isomers of the rhodium(I) eta(1)-complexes (1-9) were investigated, and the influence of the rhodium co-ligands (L=ethylene, phosphine, or carbon monoxide) was evaluated. In the case of phosphinocarbenes and carbon monoxide as a ligand, a somewhat unusual coordination mode was observed, in which a significant intramolecular Cl-->C(carbene) interaction is present. The propensity of phosphino- and aminocarbenes to behave as four electron donors was also investigated both structurally and energetically on the related eta(2)-complexes 10-18. These results as a whole emphasize the structural versatility of phosphino- compared with aminocarbene complexes.     

The first self-assembled trimetallic lanthanide helicates driven by positive cooperativity

The segmental tris-tridentate ligand L7 reacts with stoichiometric quantities of Ln(III) (Ln=La-Lu) in acetonitrile to give the complexes [Ln(2)(L7)(3)](6+) and [Ln(3)(L7)(3)](9+). Formation constants point to negligible size-discriminating effects along the lanthanide series, but Scatchard plots suggest that the self-assembly of the trimetallic triple-stranded helicates [Ln(3)(L7)(3)](9+) is driven to completion by positive cooperativity, despite strong intermetallic electrostatic repulsions. Crystallization provides quantitatively [Ln(3)(L7)(3)](CF(3)SO(3))(9) (Ln=La, Eu, Gd, Tb, Lu) and the X-ray crystal structure of [Eu(3)(L7)(3)](CF(3)SO(3))(9).(CH(3)CN)(9).(H(2)O)(2) (Eu(3)C(216)H(226)N(48)O(35)F(27)S(9), triclinic, P1, Z=2) shows the three ligand strands wrapped around a pseudo-threefold axis defined by the three metal ions rigidly held at about 9 A. Each metal ion is coordinated by nine donor atoms in a pseudo-trigonal prismatic arrangement, but the existence of terminal carboxamide units in the ligand strands differentiates the electronic properties of the terminal and the central metallic sites. Photophysical data confirm that the three coordination sites possess comparable pseudo-trigonal symmetries in the solid state and in solution. High-resolution luminescence analyses evidence a low-lying LMCT state affecting the central EuN(9) site, so that multi-metal-centered luminescence is essentially dominated by the emission from the two terminal EuN(6)O(3) sites in [Eu(3)(L7)(3)](9+). New multicenter equations have been developed for investigating the solution structure of [Ln(3)(L7)(3)](9+) by paramagnetic NMR spectroscopy and linear correlations for Ln=Ce-Tb imply isostructurality for these larger lanthanides. NMR spectra point to the triple helical structure being maintained in solution, but an inversion of the magnitude of the second-rank crystal-field parameters, obtained by LIS analysis, for the LnN(6)O(3) and LnN(9) sites with respect to the parameters extracted for Eu(III) from luminescence data, suggests that the geometry of the central LnN(9) site is somewhat relaxed in solution.     

Relativistic effects in gas-phase ion chemistry: an experimentalist's view

Gas-phase experiments provide information which, in conjunction with results from electronic structure calculations, help to unravel the critical role relativistic effects play in many areas of transition-metal chemistry. Examples include the thermochemical data of gold halides in different oxidation states, the fascinating structural properties of gold(I) complexes, the dramatic effects of ligands on the ionization energy of gold, or the binding in cationic metal-carbene complexes. Furthermore, in the context of methane functionalization, special emphasis is paid to the chemistry of cationic metal-carbene complexes, and at uncovering the mechanistic details of important carbon-heteroatom coupling reactions. It is the interplay of conducting experiments of "isolated" molecules under well-defined conditions with reliable electronic structure calculations that has considerably improved our understanding of the role relativistic effects play in the context of transition-metal chemistry, catalysis, and beyond.     

Effect of H/D-isotope substitution on the solubility and solvation thermodynamics of krypton in methanol solutions of carbamide

The solubility of gaseous krypton in CO(NH₂)₂—CH₃OH (CD₃OH) and CO(ND₂)₂—CH₃OD solutions with carbamide concentrations of up to 1.5 solvomolality units (0.026 mole fractions) was measured at 278, 288, 298, 308, and 318 K and at a partial gas pressure of 101325 Pa. The thermodynamic functions of dissolution (solvation) of krypton and the standard Setchenov coefficients were calculated. The solvation of Kr molecules increases upon deuterium substitution and with an increase in the temperature and carbamide concentration. In these solutions, specific contacts between the carbamide and methanol molecules play the predominant role.     

Gaussian approximation in the theory of MR signal formation in the presence of structure-specific magnetic field inhomogeneities

A detailed theoretical analysis of the free induction decay (FID) and spin echo (SE) MR signal formation in the presence of mesoscopic structure-specific magnetic field inhomogeneities is developed in the framework of the Gaussian phase distribution approximation. The theory takes into account diffusion of nuclear spins in inhomogeneous magnetic fields created by arbitrarily shaped magnetized objects with permeable boundaries. In the short-time limit the FID signal decays quadratically with time and depends on the objects' geometry only through the volume fraction, whereas the SE signal decays as 5/2 power of time with the coefficient depending on both the volume fraction of the magnetized objects and their surface-to-volume ratio. In the motional narrowing regime, the FID and SE signals for objects of finite size decay mono-exponentially; a simple general expression is obtained for the relaxation rate constant deltaR2. In the case of infinitely long cylinders in the motional narrowing regime the theory predicts non-exponential signal decay lnS approximately -tlnt in accordance with previous results. For specific geometries of the objects (spheres and infinitely long cylinders) exact analytical expressions for the FID and SE signals are given. The theory can be applied, for instance, to biological systems where mesoscopic magnetic field inhomogeneities are induced by deoxygenated red blood cells, capillary network, contrast agents, etc.     

On the N-exciton normalization factor

The N-ground-state-exciton normalization factor, namely 〈v| B ₀ ^N B ₀ ^dagN| v〉 = N!F _N, with B ₀ ^d ag the exact ground state exciton creation operator, differs from N! because the excitons are not perfect bosons. The quantity F_N turns out to be crucial for problems dealing with interacting excitons. Indeed, the excitons feel each other not only through the Coulomb interaction but also through Pauli exclusion between their components. A quite novel purely Pauli contribution exists in their many-body effects, which relies directly on F_N. Following procedures used in the commutation technique we recently introduced to treat interacting close-to-bosons, and in the BCS theory of superconductivity, we rederive important relations verified by the F_N's. We also give new explicit expressions of F_N valid for η = Na _x ³/ small but N ² a _x ³/ large, as F_N does not read in terms of η but Nη, the exciton number N being possibly huge in macroscopic samples. Due to this superextensivity, F_N does not appear alone in physical quantities, but through ratios like F _{N + p}/F _N. We end this work by giving the η expansion of these ratios, useful for all purely Pauli many-body effects. Received 30 May 2002 / Received in final form 12 October 2002 Published online 27 January 2003 RID="a" ID="a"e-mail: combescot@gps.jussieu.fr     

Electronic structure of three-dimensional quantum dots

We study the electronic structure of three-dimensional quantum dots using the Hartree-Fock approximation. The confining potential of the electrons in the quantum dot is assumed to be spatially isotropic and harmonic. For up to 40 interacting electrons the ground-state energies and ground-state wavefunctions are calculated at various interaction strengths. The quadrupole moments and electron densities in the quantum dot are computed. Hund's rule is confirmed and a shell structure is identified via the addition energies and the quadrupole moments. While most of the shell structure can be understood on the basis of the unperturbed non-interacting problem, the interplay of an avoided crossing and the Coulomb interaction results in an unexpected closed shell for 19 electrons. Received 5 November 2001 / Received in final form 12 November 2002 Published online 1st April 2003 RID="a" ID="a"e-mail: vorrath@physnet.uni-hamburg.de     

Statistical properties of eigenvalues for an operating quantum computer with static imperfections

We investigate the transition to quantum chaos, induced by static imperfections, for an operating quantum computer that simulates efficiently a dynamical quantum system, the sawtooth map. For the different dynamical regimes of the map, we discuss the quantum chaos border induced by static imperfections by analyzing the statistical properties of the quantum computer eigenvalues. For small imperfection strengths the level spacing statistics is close to the case of quasi-integrable systems while above the border it is described by the random matrix theory. We have found that the border drops exponentially with the number of qubits, both in the ergodic and quasi-integrable dynamical regimes of the map characterized by a complex phase space structure. On the contrary, the regime with integrable map dynamics remains more stable against static imperfections since in this case the border drops only algebraically with the number of qubits. Received 19 June 2002 / Received in final form 30 September 2002 Published online 17 Decembre 2002 RID="a" ID="a"e-mail: dima@irsamc.ups-tlse.fr RID="b" ID="b"UMR 5626 du CNRS