Static magnetization of V15 cluster at ultra-low temperatures: precise estimation of antisymmetric exchange

In this article, the low-temperature static (adiabatic) magnetization data of the nanoscopic V15 cluster present in K6[VIV15As6O42(H2O)] x 8H2O is analyzed. The cluster anion, which attracted much attention in the past, contains a triangular VIV3 array causing frustration as a function of applied field and temperature. In the analysis, a three-spin (S = 1/2) model of V15 was employed that includes isotropic antiferromagnetic exchange interaction and antisymmetric (AS) exchange in the most general form compatible with the trigonal symmetry of the system. It was shown that, along with the absolute value of AS exchange, the orientation of the AS vector plays a significant physical role in spin-frustrated systems. In this context, the role of the different components of the AS in the low-temperature magnetic behavior of V15 was analyzed, and we were able to reach a perfect fit to the experimental data on the staircaselike dependence of magnetization versus field in the whole temperature range including extremely low temperature. Furthermore, it was possible for the first time to precisely estimate the two components of the AS vector coupling constant in a triangular unit, namely, the effective in-plane component, Dperpendicular, and the perpendicular part, Dn.     

EPR spectra of V(IV) complexes and the structure of oil porphyrins

For natural bitumoids, the effects of the structure of vanadyl-porphyrin complexes on the EPR spectra were investigated. The ambiguity of the hyperfine structure (its presence or absence) corresponding to four nitrogen atoms in the spectra of oil vanadyl porphyrins correlates with the changes in the second coordination sphere of the nearest environment of the metal ion, namely, in methine bridges.     

Low temperature fluorescence spectra of atropisomeric perylene dyes

The site selection spectra of highly photostable perylene fluorescent dyes at 4.2 K in a glassy matrix of three different organic solvents (ethanol, methyl tetrahydrofuran, n-butyl acetate) are presented. The spectra ofthe two isomers are identical for a given solvent and only very minute differences are detectable between different solvents. We conclude that the influence of the matrix on the fluorescence spectra is of only minor importance. The influence of the orientation in the matrix is negligible.     

Hyperfine structure of13C and15N nuclei in EPR spectra of phosphiniminoxyls

Conclusions The EPR spectra of some chemically and electrochemically generated phosphoniminoxyls were studied. The hyperfine coupling constants on the¹³C and¹⁵N nuclei were determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 696–698, March, 1984.A calculation of the distribution of the spin density in these radicals by the PCILO method will be made later.     

Low temperature absorption spectra of KMnO4 in KClo4

The permanganate spectrum has been remeasured at liquid hydrogen and helium temperatures using spectrographs with reasonably high dispersion. Evidence is found for four absorption band systems. The first one is assigned as ¹ A ₁ ¹ T ₂ and displays a great deal of vibrational structure starting with the 0–0 line located at 18,072 cm^–1. The second transition found at 25,000 to 30,000 cm^–1 is rather featureless. The third transition with maximum at 33,000 cm^–1 shows a simple progression in quanta of 750 cm^–1. The fourth band is completely featureless with maximum intensity at 43,500 cm^–1. These findings are compared with a simplified SCF LCAO MO calculation.

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Zusammenfassung Das Permanganat-Spektrum wurde bei Temperaturen von flüssigem Wasserstoff und Helium unter Verwendung eines ausreichend auflösenden Spektrographen neu vermessen, wobei vier Absorptionssysteme gefunden wurden. Dem ersten von ihnen wurde ein ¹ A ₁ ¹ T ₂-Übergang zugeordnet; es besitzt eine ausgeprägte Vibrationsstruktur (0–0-Bande bei 18,072 cm^–1, während das folgende zwischen 25,000 und 30,000 cm^–1 kaum eine Struktur zeigt. Der dritte Übergang mit Maximum bei 33,000 cm^–1 zeigt einfache Progressionen entsprechend Quanten von 750 cm^–1. Die vierte Bande schließlich ist vollkommen strukturlos und hat ihr Maximum bei 43,500 cm^–1. Diesen Daten wurden die Ergebnisse einer einfachen SCF-LCAO-MO-Rechnung gegenübergestellt.

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Résumé Le spectre du permanganate de potassium a été réétudié aux températures de l'hydrogène et de l'hélium liquide en utilisant des spectrographes à dispersion raissonnablement élevée. On trouve la preuve de la présence de quatre systèmes de bandes d'absorption. Le premier, attribué à ¹ A ₁ ¹ T ₂, possède une forte structure vibrationnelle commencant à la bande 0–0 située à 18.072 cm^–1. La seconde transition située entre 25.000 et 30.000 cm^–1 est plutot sans structure. La troisième transition avec un maximum à 33.000 cm^–1 présente une progression simple de 750 cm^–1. La quatrième bande est complètement sans structure et a son maximum vers 43.500 cm^–1. Ces observations sont comparées avec un calcul simplifié SCF LCAO MO.

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NATO Postdoctoral Fellow 1965–66.     

Low temperature structural fluorescence spectra of tetrahydroxyanthraquinone adsorbed on silica

Adsorption of TOAQ on the surface of porous (silica gel) and non-porous (aerosil) silica modification does not cause rupture of intramolecular hydrogen bonds (IMHB). The fine structure spectra of TOAQ fluorescence on silica gel contain a set of frequencies that are characteristic of weakly perturbed molecules. A number of new spectral effects appear due to the existence of pores and centres of a nonhydroxyl character. Hydroxyl groups of aerosil take part in formation of intermolecular hydrogen bonding with the TOAQ C=O group. The bond energy of the four OH-groups of the TOAQ molecule changes non-uniformly, and the symmetry of an equilibrium nuclear configuration of TOAQ decreases.     

Low energy,low temperature mass spectra: I—selected derivatives of n-octane

The low voltage, low temperature mass spectra of a series of octane derivatives n-C₈H₁₇X with X=CH₃, OH, OCH₃, NH₂, NHCH₃, N(CH₃)₂, CO₂H, CO₂CH₃, CO₂C₂H₅, CHO and COCH₃ are reported and discussed, using arguments involving thermochemistry where appropriate. The structures of these compounds can be uniquely assigned on the basis of such mass spectra.     

双-β-萘基丙烷及其衍生物的低温荧光光谱

前文报道了合成一系列1,3-双-β-萘基丙烷的衍生物C_(10)H_7CHXCH_2CH_2C_(10)H_7,在次甲基链的第一位碳原子上分别引入OH、OAc及Cl等基团,并测定了它们的荧光光谱。从荧光光谱的结果可以看出,它们都能形成分子内激基缔合物(excimer)。最近,我们又合成了CN取代的衍生物,测定了这一系列双-β-萘基丙烷衍生物的低温荧光光谱,并计算出它们形成分子内激基缔合物所需之活化能。由于在溶液中激基缔合物的形成是扩散控制过程,在低温条件下升高温度将有利于激基缔合物的形成。