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Upali A Jayasooriya

Publications and source records attributed to Upali A Jayasooriya.

8 recordsLinked to original sources

Muon implantation of metallocenes: ferrocene.

Muon Spin Relaxation and Avoided Level Crossing (ALC) measurements of ferrocene are reported. The main features observed are five high field resonances in the ALC spectrum at about 3.26, 2.44, 2.04, 1.19 and 1.17 T, for the low-temperature phase at 18 K. The high-temperature phase at 295 K shows that only the last feature shifted down to about 0.49 T and a muon spin relaxation peak at about 0.106 T which approaches zero field when reaching the phase transition temperature of 164 K. A model involving three muoniated radicals, two with muonium addition to the cyclopentadienyl ring and the other to the metal atom, is postulated to rationalise these observations. A theoretical treatment involving spin-orbit coupling is found to be required to understand the Fe-Mu adduct, where an interesting interplay between the ferrocene ring dynamics and the spin-orbit coupling of the unpaired electron is shown to be important. The limiting temperature above which the full effect of spin-orbit interaction is observable in the muSR spectra of ferrocene was estimated to be 584 K. Correlation time for the ring rotation dynamics of the Fe-Mu radical at this temperature is 3.2 ps. Estimated electron g values and the changes in zero-field splittings for this temperature range are also reported.

Ferrous Compounds↗

Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2).

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T = 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75 +/- 1% of one unpaired electron with an upper limit of 2.5%.

Journal Article↗

Solid state effects in the IR spectrum of octahydridosilasesquioxane.

Infrared spectrum of Octahydridosilasesquioxane, in the solid state, is reported and analyzed to show the presence of significant solid state effects. This is in marked contrast with the reported Raman spectroscopic studies of this compound in the solid state where no evidence for such a proliferation of these effects were found. It is found that the normal modes with radial motion of the atoms in their normal coordinate are distinguishable from other vibrations by the distinct correlations between the band intensity and the solid state splitting observed in the IR spectrum. This new insight suggests an interchange of the literature assignments of the two modes nu27 and nu29 in the IR spectrum and a different origin to the doublet of bands in the Raman spectrum at 883 and 897 cm(-1).

Molecular Structure↗

Vibrational spectroscopic analysis of silicones: a Fourier transform-Raman and inelastic neutron scattering investigation.

An inelastic neutron scattering spectrum of a poly(dimethylsiloxane) (PDMS) is reported, and a spectrum simulated using a monomer molecular unit as a model for comparison. FT-Raman spectra of a series of PDMS derivatives are reported and structure spectra correlations are shown to exist for the estimation of (a) PDMS average chain length, (b) ratio of the number of monofunctional units to quadrifunctional units in silicone resins, and (c) the percentage weight of PDMS in silicone emulsions.

Journal Article↗

Molecular sensors using a resonance Raman template.

The potential use of resonance Raman spectroscopy as a molecular sensing tool is illustrated using a metalloporphyrin template and pyridine as an analyte. The equilibrium binding constant for the axial binding of pyridine to zinc tetraphenylporphyrin has been measured using resonance Raman spectroscopy. Although no new peaks are observed and the porphyrin peaks do not shift position, the quantification is made possible by the selective resonance enhancement of the template vibrations. The value for log k was determined by resonance Raman to be 3.65 +/- 0.32, which compares well with previously published values estimated using absorption data. Values for log k were determined for a series of related compounds, the picolines, and these also compare favourably with those previously reported.

Journal Article↗