The Dirac equation in quantum chemistry: strategies to overcome the current computational problems

A perspective on the use of the relativistic Dirac equation in quantum chemistry is given. It is demonstrated that many of the computational problems that plague the current implementations of the different electronic structure methods can be overcome by utilizing the locality of the small component wave function and density. Possible applications of such new and more efficient formulations are discussed.     

A dithienylethene-tethered beta-cyclodextrin dimer as a photoswitchable host

The binding of TSPP by a dithienylethene-tethered beta-cyclodextrin dimer can be altered reversibly by irradiation with light.     

In-beam spectroscopy of 253, 254No

In-beam conversion electron spectroscopy experiments have been performed on the transfermium nuclei ^{253, 254}No using the conversion electron spectrometer SACRED in nearly collinear geometry in conjunction with the gas-filled separator RITU at the University of Jyv?skyl?. The experimental setup is discussed and the spectra are compared to Monte Carlo simulations. The implications for the ground-state configuration of ²⁵³No are discussed. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: rdh@ns.ph.liv.ac.uk RID="b" ID="b"Present address: GANIL, F-14021 Caen, France. RID="c" ID="c"Permanent address: IReS Strasbourg, IN2P3-CNRS, F-67037-Strasbourg, France. RID="d" ID="d"Present address: CEA/DIF DCRE/SDE/LDN F-91680 Bruyeres-le-Chatel. RID="e" ID="e"Present address: Daresbury Laboratory, Daresbury WA4 4AD, UK. RID="f" ID="f"Permanent address: IPN Lyon, IN2P3-CNRS, F-69037 Lyon, France.     

Fast fission phenomena: A possible intermediate time scale between deep inelastic reactions and compound nucleus formation

The change of the FWHM of the mass distribution of the fission products as a function of angular momentum is interpreted as a signature for a mechanism which is intermediate between compound nucleus formation and deep inelastic reactions. An intermediate composite system is assumed to be formed during the reaction, which undergoes fission. This kind of mechanism can therefore be called fast fission phenomena. It is related to the existence of a long lifetime component in déep inelastic reactions. Within the framework of a simple statistical model a qualitative as well as a quantitative estimate is done for a particular system. The conditions under which such a mechanism can be observed are discussed.     

Induction asymétrique—IV: Etude des modes de reconnaissance intermoléculaire des β-aminocétones aromatiques prochirales,par les réactifs de réformatsky. Mise en évidence d'un phénoméne de participation

In the reaction of Reformatsky reagents (R-CHZnBr-CO₂R') with aromatic β-aminoketones (C₆H₅-CO-CH₂-CH₂-NR″₂, mixtures of erythro and threo diastereomeric amino-hydroxyesters, with the former predominating, were obtained.The proposed bicyclic transition states involve the participation of the neighbouring nitrogen atom, and support the direction and the magnitude of the observed asymmetric induction. The relative stabilities of diastereomeric transition states are discussed in terms of steric and electronic effects.     

Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order M?ller-Plesset perturbation theory, fourth-order M?ller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values.     

Quantitative measurement of temperature by proton resonance frequency shift at low field: a general method to correct non-linear spatial and temporal phase deformations

MRI thermometry methods are usually based on the temperature dependence of the proton resonance frequency. Unfortunately, these methods are very sensitive to the phase drift induced by the instability of the scanner which prevents any temperature mapping over long periods of time. A general method based on 3D spatial modelling of the phase drift as a function of time is presented. The MRI temperature measurements were validated on gel samples with uniform and constant temperature and with a linear temperature gradient. In the case of uniform temperature conditions, correction of the phase drift proved to be essential when long periods of acquisition were required, as bias could reach values of up to 200 degrees C in its absence. The temperature uncertainty measured by MRI was 1.2 degrees C in average over 290 min. This accuracy is coherent with the requirements for food applications especially when thermocouples are useless.     

The t#-property for integral domains

Generalizing work of Gilmer and Heinzer, we define a t#-domain to be a domain R in which for any two distinct subsets and of the set of maximal t-ideals of R. We provide characterizations of these domains, and we show that polynomial rings over t#-domains are again t#-domains. Finally, we study overrings of t#-domains.     

Reflection anisotropy spectroscopy: A new probe for the solid-liquid interface

Introducing reflection anisotropy spectroscopy (RAS) as a new probe for solid-liquid interfaces, we present results for the Au(110)/electrolyte interface which serves as a model system. We demonstrate that RAS is sensitive to surface phase transitions, step morphology, and electronic surface states. Using an empirical approach, the RA spectra are reproduced and features are identified which reflect the known character of the bias voltage driven (2x1) to (1x1) phase transition. RAS is established as an experimental technique to probe the electronic structure of solid-liquid interfaces in real time to study a wide range of interface properties.