Generic implementation of semi-analytical CI gradients for NDDO-type methods

Generic semi-analytical energy gradients are derived and implemented for NDDO-type methods, by using numerical integral and Fock matrix derivatives in the context of an otherwise analytical approach for configuration interaction (CI) and other non-variational treatments. The correctness, numerical precision, and performance of this hybrid approach are established through comparisons with fully numerical and fully analytical calculations. The semi-analytical evaluation of the CI gradient is generally much faster than the fully numerical computation, but somewhat slower than a fully analytical calculation, which however shows the same scaling behavior. It is the method of choice whenever a fully analytical CI gradient is not available due to the lack of analytical integral derivatives. The implementation is generic in the sense that it can easily be extended to any new NDDO-type Hamiltonian. The present development of a semi-analytical CI gradient will facilitate studies of electronically excited states with recently proposed NDDO methods that include orthogonalization corrections. Dedicated to Professor Karl Jug on the occasion of his 65th birthday     

Implementation of a general multireference configuration interaction procedure with analytic gradients in a semiempirical context using the graphical unitary group approach

The graphical unitary group approach has been applied in an efficient implementation of a general multireference configuration interaction (MRCI) method for use with small active molecular orbital spaces in a semiempirical framework. Gradients can be computed analytically for molecular orbitals from a closed-shell or a half-electron open-shell Hartree-Fock calculation. CPU times for single point energy and gradient calculations are reported. The code allows MRCI geometry optimizations of large molecules, as illustrated for the singlet ground state and the four lowest triplet states of fullerene C(76).     

The Ideal Ionic Liquid Salt Bridge for the Direct Determination of Gibbs Energies of Transfer of Single Ions,Part I: The Concept

Described is a procedure for the thermodynamically rigorous, experimental determination of the Gibbs energy of transfer of single ions between solvents. The method is based on potential difference measurements between two electrochemical half cells with different solvents connected by an ideal ionic liquid salt bridge (ILSB). Discussed are the specific requirements for the IL with regard to the procedure, thus ensuring that the liquid junction potentials (LJP) at both ends of the ILSB are mostly canceled. The remaining parts of the LJPs can be determined by separate electromotive force measurements. No extra‐thermodynamic assumptions are necessary for this procedure. The accuracy of the measurements depends, amongst others, on the ideality of the IL used, as shown in our companion paper Part II.     

β-Octafluorinated tetrakis(ethoxycarbonyl)porphyrin

Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ).     

Size Matters! On the Way to Ionic Liquid Systems without Ion Pairing

Several, partly new, ionic liquids (ILs) containing imidazolium and ammonium cations as well as the medium‐sized [NTf₂]^? (0.230 nm³; Tf=CF₃SO₃^?) and the large [Al(hfip)₄]^? (0.581 nm³; hfip=OC(H)(CF₃)₂) anions were synthesized and characterized. Their temperature‐dependent viscosities and conductivities between 25 and 80 °C showed typical Vogel–Fulcher–Tammann (VFT) behavior. Ion‐specific self‐diffusion constants were measured at room temperature by pulsed‐gradient stimulated‐echo (PGSTE) NMR experiments. In general, self‐diffusion constants of both cations and anions in [Al(hfip)₄]^?‐based ILs were higher than in [NTf₂]^?‐based ILs. Ionicities were calculated from self‐diffusion constants and measured bulk conductivities, and showed that [Al(hfip)₄]^?‐based ILs yield higher ionicities than their [NTf₂]^? analogues, the former of which reach values of virtually 100 % in some cases.From these observations it was concluded that [Al(hfip)₄]^?‐based ILs come close to systems without any interactions, and this hypothesis is underlined with a Hirshfeld analysis. Additionally, a robust, modified Marcus theory quantitatively accounted for the differences between the two anions and yielded a minimum of the activation energy for ion movement at an anion diameter of slightly greater than 1 nm, which fits almost perfectly the size of [Al(hfip)₄]^?. Shallow Coulomb potential wells are responsible for the high mobility of ILs with such anions.     

Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo (F₁₅CMn（V）-oxo),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo(F₁₀CMn（V）-oxo),5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F₅CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F₀CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.     

Direct observation of slow morphological transformations and wetting behavior of pulsed laser deposited sub-monolayer gold on (0 0 0 1) sapphire in atmosphere

Using high-resolution atomic force microscope we observed in ambient atmosphere the slow morphological transitions of the incipient adlayer of gold grown on (0 0 0 1) sapphire substrate by pulsed laser deposition. The equivalent average uniform thickness of the gold deposition was about 0.55 Å, which is about one-fourth of its monolayer. A dynamic simulation revealed that about 10% of the gold was implanted into the substrate up to the depth of about 3.3 nm and the top monolayer of the sapphire surface was almost completely depleted of oxygen atoms due to the preferential sputtering by the plume particles. The gold adlayer transformed into a labile phase which enhanced the surface roughness and had a preferred orientation of a wavy structure during 24 h of the deposition. The auto-correlation function of this wavy structure in labile metastable phase revealed two-fold symmetry and provided a preferential size of about 4 nm (peak to peak) with a mean separation of 8 nm. At the end of about 6 days this phase was found to completely transform into an apparently de-wetted phase of beads with average in-plane diameter of ∼20 nm and height of ∼7 nm having large size distribution. Each bead was seen to have coating of a concentric corona layer, which might be that of the condensed moisture or other gaseous species from atmosphere because subjecting these samples to vacuum removed this layer. These observations shed light on the dynamics of the pulsed laser deposited metastable gold adlayer in the incipient stage of its growth on sapphire and their wetting or de-wetting mechanisms in ambient atmosphere.     

Influence of the dynamic ergodic divertor on the density limit in TEXTOR

A significant influence of the dynamic ergodic divertor (DED) on the density limit in TEXTOR has been found. In Ohmic discharges, where without DED detachment normally arises at the density limit, a MARFE (multifaceted asymmetric radiation from the edge) develops when the DED is operated in a static regime. The threshold of the MARFE onset in the neutral beam heated plasmas is increased by applying 1 kHz ac DED at the high-field side. The theoretical predictions based on the parallel energy balance taking poloidal asymmetries into account agree well with the experimental observation.     

Turbulence investigations during ergodic divertor operation with induced 2/1 tearing mode

Within the last year of TEXTOR operation a major part of the experiments were dedicated to the interaction of the ergodized plasma edge, induced by the dynamic ergodic divertor (DED), with the core plasma. Systematic experiments are performed in the 3/1 configuration of the DED. Depending on , the DED generates a locked 2/1 mode in the plasma at a critical current in the DED coils. Different diagnostics were used to measure the plasma response in the core and edge. The investigations in this paper are focused on the measurement of density fluctuation and the analysis of the coherent-mode structure outside the q = 2 surface using O-mode poloidal correlation reflectometry. A reduction of the quasi-coherent mode amplitude and frequency is observed, caused by the 2/1 mode together with a decrease of the density scale length. Moreover, the deduced poloidal rotation velocity at the q = 3 surface changes from the electron to the ion diamagnetic drift direction with the onset of the 2/1 island. Also a reduction of the density fluctuations is observed as well as a decrease in the poloidal correlation length. From Ar-injection a delayed inward propagation of the emission maximum is observed for different Ar ionization stages when the 2/1 mode is generated.Similar experiments with a slowly rotating DED show that the steepened density gradients are spatially localized and confirm the hypothesis that the 2/1 mode is responsible for the observations.Presented at the Workshop Electric Fields Structures and Relaxation in Edge Plasmas, Nice, France, October 26–27, 2004.     

Are protons involved in the hydrogen-induced surface conductivity of diamond(001)?

We have investigated the mechanism underlying the surface conductivity observed for synthetic diamond(001) samples. It is found that (1) the surface conductivity depends on the pressure of the surrounding gas atmosphere, (2) the temperature dependence can be described as being due to a thermally activated process and (3) a chromogeneous WO₃ cathode turns color from transparent to blue and gas bubbles develop underneath the cathode if an electrical dc current is passed through such an arrangement. In contrast, the complementary WO₃ anode neither changed color nor were gas bubbles observed. One concludes that hydrogen develops at the negatively biased WO₃-diamond interface, recombining to gaseous H₂. However, most of the hydrogen invades the WO₃ cathode coloring it blue, thereby clearly indicating the involvement of protons. Though the conductivity crucially depends on temperature, time and history of a sample, the resistances of various and even differently prepared diamond specimens covering eleven orders of magnitude can be scaled onto one master curve reflecting a thermally activated behavior. Taken together, we propose that the mechanism of the diamond(001) surface conductivity as observed under ambient conditions is at least partly due to proton conduction. Received: 13 April 2000 / Accepted: 31 July 2000 / Published online: 22 November 2000