Werner Haberditzl

Eichinvariante Berechnung des Diamagnetismus und der chemischen Verschiebung, 1. Mitt.: Ableitungeiner eichin varianten Theorie und ihre Anwendung auf zweiatomige Moleküle und lokalisierte Orbitale

Based on the work ofRebane3 andStaemmler4, a general method has been developed for the approximation of theVan-Vleck-term χ P and theRamsey-term σ P (high frequency contribution of the susceptibility and the chemical shift). An advantage of the method is its complete independence of the coordinate origin. This feature does not depend on approximations in the wave function. Furthermore it is not necessary to construct the perturbated wave function for the calculation of . As these terms are obtained from a power series, only the knowledge of the following one-electron-integrals is necessary:

Eichinvariante Berechnung des Diamagnetismus und der chemischen Verschiebung@@@Gauge-invariant calculation of diamagnetism and chemical shift III.: Incre-mentary calculation of the susceptibility-and shielding tensors of protons and13C-nuclei of polyatomic molecules based on a semiclassical model: 3. Mitteilung: Inkrementre Berechnung der Suszeptibilitts-und Abschirmtensoren von Protonen und13C-Kernen mehratomiger Molekle auf der Grundlage eines halbklassischen Modells

\begin{gathered} \left\langle {\varphi a\left| {X^i Y^j Z^k } \right|\varphi _b } \right\rangle for \chi ^P and \hfill \\ \left\langle {\varphi a\left| {(X^i Y^i Z^k )r^{ - 3} } \right|\varphi b} \right\rangle for \sigma ^P \hfill \\ \end{gathered}

Eichinvariante Berechnung des Diamagnetismus und der chemischen Verschiebung

(a,b-Slater-type orbitals).

Eichinvariante Berechnung des Diamagnetismus und der chemischen Verschiebung@@@Gauge-invariant calculation of diamagnetism and chemical shift IV: Incrementary calculation of the diamagnetism of unsaturated hydrocarbons: 4. Mitt.: Inkrementre Berechnung des Diamagnetismus ungesttigter Kohlenwasserstoffe

Expressions are derived for the decomposition of tensorial properties into additive increments.In the second part of the paper calculations of σH andCH for LiH and of the susceptibilities for Li2, BH, HF, CO, F2, and LiF are presented. The contributions of the various LMOs to χ, χP andg-values are discussed. The results are compared to those obtained from coupledHF-perturbation theory and to experimental values where available. The values for χ are in good agreement with the experiment and—except for BH—with theHF-perturbation theory, however deviations are found in some molecules for Δχ andg-values and traced back to specific electronic features.

Die Berechnung von Einelektronen-Integralen in der SCF-Xα-SW-Methode: II. Einelektronen-Eigenschaften

The procedure derived in1–6 was used to calculate the magnetic susceptibilities and the magnetic shielding of a series of diamagnetic molecules (CH4, C2H6, C2H4, C2H2, and HCN). The model requires only the knowledge of the unperturbed electron density. An incrementary treatment of the susceptibility-and shielding tensors is based on a partition of the electron density into localized parts.The values obtained by this procedure are in good agreement with experimental results in the case of susceptibilities and magnetic protonshieldings. The results for the13C-shielding however are not satisfactory.

Die Berechnung von Einelektronen-Integralen in der SCF-Xα-SW-Methode: I. Die Normierung

Based on the combination ofPars-Orbitals (PO) the LCPO-MO-Method has been described for the quantum chemical treatment of large molecules which are divided in reasonable fragments. The secular matrix constructed from the Eigenvalues and parameters of the molecular fragments has a characteristic block-form. The dimension of the secularproblem can be reduced and depends on the used approximations. The resulting method is demonstrated for naphthalene.

Anomalies in the Magnetic Circular Dichroism of Benzene in Cyclohexane

The procedure described in1,2 was used to calculate the magnetic susceptibility contributions of C-H bonds to the diamagnetism of various hydrocarbons. It was found a correlation between these C-H-bond contributions and the bond lengths. The transferability of the evaluated C-H-bond susceptibilities from one molecule to another is discussed.

Zur magnetooptischen Rotationsdispersion des Anthracens in verschiedenen Lösungsmitteln

The procedure derived in1–4 was used to calculate the magnetic susceptibilities of a series of unsaturated hydrocarbons (propene, isobutene, 1-butene, cyclohexene, butadiene,trans-1,3,5-hexatriene). The difference δχ between the measured and computed susceptibilities of these molecules is discussed. The discussion shows, that there is no correlation existing between the difference δχ and the presumed delocalisation effects.