A variational coupled cluster theory for closed shells using a propagator modification procedure

A general partial summation method for including arbitrary classes of diagrams to all orders in the coupled cluster based size consistent energy functional for closed shell states is developed. Since the various reduced density matrices which appear in the energy functional are essentially the time-independent analogues of the corresponding many body Green functions, it is possible to derive Dyson-like equations for these quantities. By expanding the associated proper self energy parts in terms of the T-amplitudes, one can carry out partial summations in the reduced density matrices and thus in energy. At a higher level, higher order terms in a proper self energy can also be generated by renormalizing the internal propagators in it, and considering only the irreducible self-energy terms.     

Kinetics of thermal dehydration of La(III) and Yb(III) complexes with ortho-vanillin oxime

The analysis of dehydration of the complexes, [La(C₈H₈NO₃)₃.2H₂O] and [Yb(C₈H₈NO₃)₃.3H₂O] for the evaluation of kinetic parameters (Z, E &S ^*) and mechanism of dehydration by non-isothermal methods are reported. The complexes decompose in three well defined steps involving random nucleation mechanism. First two steps involving the dehydration and the third step the loss of the ligand moiety. The intermediates formed during decomposition were found to be unstable for carrying out any significant studies.

---

Zusammenfassung Zwecks Ermittlung der kinetischen Parameter (Z, E undS ^*) und des Mechanismus der Dehydratierung durch nichtisotherme Verfahren wird die Analyse der Dehydratierung der Komplexe [La(C₈H₈NO₃)₃·2H₂O] und [Yb(C₈H₈NO₃)₃·3H₂O] beschrieben. Die Komplexe zersetzen sich in drei gut definierten Schritten mit Random-Keimbildungsmechanismus. Die ersten zwei Schritte beinhalten die Dehydratierung, der dritte Schritt den Verlust der Liganden. Die wÄhrend der Zersetzung entstandenen Zwischenprodukte erwiesen sich für jegliche signifikante Untersuchung als zu unstabil.

     

Vinyl polymerization of acrylonitrile by the Ce(IV)-glucose redox system

Aqueous polymerization of acrylonitrile (M) initiated by the Ce(IV)-glucose (R) redox system has been studied under nitrogen in the temperature range of 30–40 °C. The rate of polymerization (Rp) is proportional to [M]², [R] and inversely proportional to [Ce(IV)]. The rate of ceric ion disappearance is proportional to [R] and [Ce(IV)]. The end group in the polymer is characterised by IR spectra. A suitable kinetic scheme has been proposed and explained in the light of these experimental findings.     

Complexation of 6-Deoxy-6-(aminoethyl)amino-β-cyclodextrin with Sodium Cholate and Sodium Deoxycholate

In order to study its guest binding and the inclusion phenomena, 6-deoxy-6-(aminoethyl)amino--cyclodextrin (CDN) was synthesised and its binding properties examined. The complexation phenomena of sodium cholate (NaC) and sodium deoxycholate (NaDC) with CDN has been monitored by the NMR method using ¹³C chemical shift data. The method of continuous variation Job's method has been used to determine the stoichiometry of these supramolecular complexes. The Job's plot confirms the 1 : 1 supramolecular complex for NaC: CDN and the 1 : 2 supramolecular complex for NaDC: CDN. The interaction of NaC and NaDC with CDN has been obtained through two-dimensional Rotational Nuclear Overhauser Effect Spectroscopy (ROESY) NMR. Equilibrium constants were also obtained from ¹³C chemical shift data (C-1, C-3 & C-4) at different pH values (7, 9, & 11).     

Synthesis and Spectroscopic Characterisation of Six-Coordinate Complexes of Oxovanadium(V)

Complexes of the types VO(L)(R-deaH), VO(R-dea)(LH), and VO(L)(OGOH)[L = deprotonated form of N-(1-hydroxyethyl) naphthaldimine; R-dea = deprotonated form of a N-substituted diethanolamine, with R = H or Ph; G = CH₂CH₂, CHMeCHMe, CMe₂CMe₂, CHMeCH₂CMe₂, CMe₂CH₂CH₂CMe₂] have been prepared by the equimolar reactions of VO(OPr ⁱ )₃, LH₂, and an appropriate diethanolamine or glycol in benzene. All of these coloured solid complexes have been characterised by elemental (C, H, N, and V) analyses and by spectroscopic (i.r., electronic, ¹H-, ⁵¹V-n.m.r) studies. The relative lability of the hydroxy group(s) of N-(1-hydroxyethyl)naphthaldiamine, diethanolamine, and glycol has also been investigated.