Inclusion of dynamic σ-π polarization in π-electronab initio calculations

Summary A method is presented, whereby dynamic - polarization, i.e. the correlation effect expressed by simultaneous (-*, -*) excitations, can be approximately included in a multi-reference configuration interaction (MRCI) or multi-configurational self-consistent field (MC-SCF) calculation, without need to explicitly correlate the sigma orbitals. The method, which we call the capacitance matrix method, is based on the use of conventional one-electron integrals, from which a polarization potential (SPP) contribution is computed and added to the one- and two-electron Hamiltonian. In the present form, the method requires one parameter for each type of atom, and one for each type of bond. These parameters were adjusted to reproduce the dynamic - polarization energy, computed by restricted multi-reference CI calculations, of a number of states of different hydrocarbons, and the agreement was within a few percent. Using the same parameters in CAS (Complete Active Space) SCF calculations of various states of benzene gives excitation energies, when SPP is included, which is comparable to those obtained by much more elaborate MRCI calculations.     

A theoretical determination of the electronic spectrum of formaldehyde

Summary The electronically excited states of formaldehyde are examined by means of multiconfigurational second-order perturbation (CASPT2) theory with extended ANO-type basis sets. The calculations comprised five valence excited states plus all singlet 3s, 3p, and 3d members of the Rydberg series converging on the first ionization. The computed vertical excitation energies were found to be within 0.2 eV of the available experimental energies. Full geometry optimization has been performed for five valence excited states. Assuming a planar geometry, the 0-0 transition for the valence¹A₁( *) state is calculated to appear near 7.9 eV, close to the (n _y 3p) region. This state is, however, not planar and the true adiabatic energy is 7.4 eV, which is 2.3 eV below the corresponding vertical transition.     

Does CH prefer a C2v rather than a Cs structure?

The closely related C_s ( 1 ) and C_2v ( 3 ) structures of CH have been reinvestigated at many ab initio levels using MP2/6-31G** and MP2/6-311 + + G(2df, 2pd) geometries. The largest basis sets employed were 6-311G(3df, 2p), 6-311 + + G(3df, 3pd), and the Dunning “correlation consistent” polarized triple-split valence basis set (cc-pVTZ). Electron correlation was probed at the MP4 level, but the QCISD method was also used with the largest basis sets. While electron correlation favors 3 over 1 by about 2 kcal/mol, the correlated relative energies with all basis sets employed range from 0.36–1.03 kcal/mol in favor of 1 . The best estimate of this difference, 0.86 kcal/mol, is essentially identical with the (scaled) zero-point energy difference, 0.84 kcal/mol, favoring 3 over 1 . These results indicate that 1 and 3 have almost exactly the same energy at 0 K. Our best value for the dissociation energy of CH is 42.0 kcal/mol [QCISD(T)/6-311 + + G(3df, 3pd)//MP2(fu)/6-311 + + G(2df, 2pd), corrected to 298 K], which agrees very well with the experimental value. © 1992 by John Wiley & Sons, Inc.     

Determination of C1−C4 fatty acids as p-bromophenacyl esters using glass-capillary gas chromatography and electron-capture detection

Summary A method for the determination of low relative molecular mass carboxylic acids (C₁–C₄) in water is reported. The acids are converted to p-bromophenacyl esters prior to a glass-capillary gas chromatographic separation. By utilizing electron-caputre detection the detectability is substantially improved compared to flame-ionization detection. A comparison of three different ways to treat the water samples and to produce the derivatives is made. It is shown that the , p-dibromoacetophenone reagent decomposes to a small extent which limits the utility of the reagent. Nevertheless a detection limit for formic acid of approximately 2.5 mgl^–1 is obtained. The method is applied to the determination of formic and acetic acids in a paper kraft water sample.     

On the existence of interior solutions in general relativity

The existence problem of matter sources for given stationary axisymmetric solutions of Einstein's vacuum field equations is investigated. The existence of sources of a differentially or rigidly rotating perfect fluid can be proved at least in the neighborhood of boundary surfaces if these can be chosen suitably (theorem). In particular, there exist such half-local perfect fluid sources for the Kerr metric. Hence the existence of a global regular Kerr-interior solution cannot be excluded by local considerations in an arbitrarily small neighborhood of a possible boundary.Work supported in part by the Deutsche Forschungsgemeinschaft.     

The Intrusion of the Meissen Pluton (Elbe Valley-Zone): Evidence from Geochemical and Isotopic Data

Abstract

Geochemical and mineralogical investigations of plutonic rocks from the Meiβen massif indicate different magmatic evolution trends of the Freital sequence as well as for the central part of the complex Constant ε-Nd_T-345 values of ?1.5 of the Freital sequence and major/trace element data point to a fractional crystallization process. Based on ε-Nd values, ¹⁴⁷Sm/¹⁴⁴Nd ratios as well as on geochemical data affinities to alkali basalts cannot be excluded.

Analogous conclusions have been drawn regarding mineral chemical data [10] and cathodoluminescence spectra of apatite [13]. Assimilation of old continental crust, reflected by relics of apatite and zircon, may be the reason that the ε-Nd values plot at the lower end of the “mantle array”. The pyroxene-monzodiorite from Gröba belongs to the same source environment as the Freital sequence (Nd-characteristics).

The geological evolution of the central part of the studied plutonic complex is completely different to the Freital sequence: most of the intrusions show signatures of open system fractionation processes. The ε-Nd_T-345 value of ?1.46 of the Leuben monzonite indicates a narrow relation to the Freital sequence, whereas the ε-Nd_T-345 value of +2.27 of the Spitzgrund monzonite either reflects the derivation of another basic material then the Freital-type or the participation of other mixing component(s) from geologically young crust.

Fabric and mineral chemical investigations of the porphyry-like granite GII point to a mixing process of basic xenocrysts, resembling the corresponding minerals of the Freital sequence, and granite melts [10]. Large amounts of old zircon cores [11] indicate the inheritance of continental crust components by the Hauptgranit. Isotopic investigations on various granitic samples (GII, Hauptgranit and Riesensteingranit) reflect an increasing trend towards the crustal source(s) of their parental melts. The ε-Nd_T-345 values are ?3.75, ?4.16 and ?6.13, respectively.

Chemical parameters and the ε-Nd_T value of the Riesensteingranit agree with data of granites from the Saxonian Granulite Massif (see e.g. Wand et al. [8]; von Quadt, 1992). Thus, it may be possible that both granite types derived from similar sources.     

Geochemical investigation of alluvial sediments: validation of ICP-OES determination of heavy metals. A case study from the Utrata River Valley (central Poland)

The development and validation of a reliable analytical procedure for the determination of selected metals (Cd, Cr, Cu, Pb, Zn and Mn) in sediments accumulated in the Utrata River (Poland) is described. The aqua regia extraction followed by inductively coupled plasma optical emission spectrometry (ICP-OES) was used for this purpose. The optimized analytical procedure was validated, and adequate quality control actions were implemented in order to provide reliable data. The precision under’ within-laboratory’ reproducibility conditions was estimated from duplicate analysis. Certified reference material (CRM) was used in order to evaluate the accuracy of the results regarding the sewage sludge amended soil CRM 143R. The detection limits for all elements of interest were well-below their content in the investigated sediment samples. The obtained reliable data could be used for assessment of the relationship between human economic activity in the past and the geochemical features of the sediments.     

Inter-laboratory exercise with an aim to compare methods for 90Sr and 239,240Pu determination in environmental soil samples

In order to deliver reliable results for a multitude of different scenarios, e.g. emergency preparedness, environmental monitoring, nuclear decommissioning and waste management, there is a constant process of method development in the field of radioanalytical chemistry. This work presents the results of a method comparison exercise aimed at quantifying ⁹⁰Sr and ^239,240Pu in environmental soil samples, with the intention of evaluating the performance and applicability of different methods. From the methods examined in this work, recommendations are given in order to find a radioanalytical measurement procedure, for ⁹⁰Sr and ^239,240Pu analysis, which is fit-for-purpose for a particular scenario.

     

Oxidation stability of various Ti-alloys

Since titanium metal first became a commercial reality in 1950, corrosion resistance has been an important consideration in its selection as an engineering structural material. Titanium has gained acceptance in many media where its corrosion resistance and engineering properties have provided the corrosion and design engineer with a reliable and economic material. Titanium, like any other metal, is subject to corrosion in environments of air, oxygen, moisture, and so on. In this work, high-temperature stability of Ti and various Ti-alloys (by ASTM standard) was investigated. The best results showed that for Ti-Gr.5 alloy, the oxidation at 800 °C was 3.39% and at 900 °C 8.35%. For the comparison, commercial pure Ti-alloys Ti-Gr.2 and Ti-Gr.37 containing Al were used, whereas the oxidation resistance was much worse.     

Novel 1,2,4-Triphosphole, 1,2,3-Triphosphetene and Azaphospholene Derivatives from N -Heterocyclic Carbenes and Phosphaalkynes

The stable singlet carbenes N,N '-bis(2,2-dimethylpropyl)-benzimidazolin-2-ylidene 1 and 1,3,4,5-tetramethylimidazol-2-ylidene 2 react with phosphaalkynes P L C-- t Bu ( 3a ) or P L C--N i Pr 2 ( 3b ) regioselective to give the aromatic 1,2,4-triphosphole derivatives ( 1 or 2 + 3a M 6a or 6b , respectively) or 1,2,3-triphosphetene ( 1 + 3b M 7 ) or azaphospholene ( 2 + 3b M 9 ) in almost quantitative yields. The mechanisms of the surprising formation of compound 9 under C--H-activation was studied by quantum chemical DFT calculations.