Nuclear moments as a probe of electronic structure in material, exotic nuclear structure and fundamental symmetry

We report our studies in various fields of Physics through nuclear moments utilizing the β-NMR technique, including material sciences, nuclear structures and fundamental symmetries. Especially, we focus on the recent progress in the studies on the electronic structure in Pt through Knight shifts of various impurities, lattice locations of impurities, electric field gradients, the analysis of nuclear spin in terms of its components, anomaly in the spin expectation value for ⁹C-⁹Li mirror pair, the G-parity conservation law, and the Ramsey resonance on UCN for future neutron EDM measurements.     

Paramagnetic transition metal carbonyls : IV. ESR study of anions derived from (CO)5MnPbPh3 and (CO)4CoPbPh3 by high energy radiation

Exposure of (CO)₅MnPbPh₃ to ⁶⁰Co γ-ray at 77 K gave one major paramagnetic species detectable by ESR spectroscopy. This exhibited an anisotropic hyperfine interaction with ⁵⁵Mn, near free-spin g-values, and a small, almost isotropic coupling to ²⁰⁷Pb. The form of the A(⁵⁵Mn) and g-tensor components suggest an orbital of d_z² symmetry on manganese for the unpaired electron, but this cannot be directed along the MnPb bond since the ²⁰⁷Pb hyperfine coupling indicates a very low spin-density on lead. We suggest that the centre is formed by electron addition to manganese to give a formal d⁷ centre, with concomitant loss of one equatorial carbonyl ligand. We defind z as the direction of the lost ligand. A second centre, detected at high gain, having a large hyperfine coupling to ²⁰⁷Pb and a 31 G coupling to ⁵⁵Mn is tentatively identified as the parent cation.In marked contrast, the molecule (CO)₄CoPbPh₃ gave a single centre having comparable ⁵⁹Co hyperfine and g-tensor components, but also a very large hyperfine coupling to ²⁰⁷Pb (ca. 3300 G). Thus, in this case, an electron gain centre (d⁹) has been formed, the electron being accomodated in the highest MO having a large d_z² component on cobalt (z being now the CoPb direction).Reasons for the adoption of these different structures are discussed.     

Definitive evidence that the ESR spectrum observed during photolysis of Mn2(CO)10 in THF is due to octahedral high-spin (d5) manganese(II)

The reassignment to a manganese(0) quartet state by C.L. Kwan and J.K. Kochi (J. Organometal. Chem., 101 (1975) C9) of the ESR spectrum obtained during photolysis of Mn₂(CO)₁₀ in THF is shown to be in error; computer simulation of the X-band spectrum and observation of the S-band spectrum confirm our previous assignment to sextet manganese(II) and chemical and IR evidence indicate the presence of [Mn(CO)₅]^? as a counter ion.     

Interactions in water-alcohol mixtures studied by NMR and infrared spectroscopy

By using low temperatures and largely deuterated solvents, the rate of OH proton exchange for aqueous solutions of alcohols is reduced sufficiently to give separate NMR signals from water and alcohol OH protons. The limiting shifts for dilute alcohols in water are down-field of both the water resonance and those of the pure alcohols. This contrasts with the limiting shift for water in the alcohols, which is to high field of the bulk water resonance. The resonance shifts initially to low fields as [ROH] increases, the rate of shift being greatest for t-butyl alcohol. For dilute aqueous solutions, all the alcohols reduce the total concentration of free OH groups, as judged by the overtone infrared spectra. Some of these results are interpreted in terms of a scavenging of free OH groups by the excess lone-pairs of the alcohol molecules. An extra, temperature dependent, down-field shift in the water proton resonance induced by t-butyl alcohol is assigned to a clathrate cage effect.     

Electron spin resonance studies of the radiolysis of bi-π-cyclopentadienylalkyls of molybdenum and tungsten

Exposure of (C₅H₅)₂MO(CH₃)₂ and (C₅H₅)₂W(CH₃)₂, prepared from the corresponding dichlorides, to ²⁰Co γ-rays at 77 K gave H₂C.CML₃ carbene species characterised by their ESR spectra, together with a central feature possibly due to the parent cations. Dilute solutions in CD₃OD gave features assigned to the parent anions which were converted on bleaching with visible light into methyl radicals, and H₂C.ML₃ radicals. From the magnitude of the ¹H and ¹⁸³W hyperfine coupling constants, it is deduced that the SOMO for H₂C.WL₃ radicals is strongly localised on carbon.Dilute solutions in aqueous sulphuric acid also gave species with A(2H) = 20 G, identified as the carbene derivatives, H₂C.Ml₃. These were formed on annealing, as signals assigned to HSO₄ · radicals were lost.     

The use of amorphous and microcrystalline silicon for silicon heterojunction bipolar transistors

The modification of the emitter structure of silicon bipolar transistors results in more freedom in the choice between sometimes conflicting device parameters. The approach followed in this work is the use of an amorphous silicon (a-Si:H) or microcrystalline silicon (c-Si) emitter, creating a real heterojunction with the crystalline silicon base. Due to the larger bandgap of these emitter materials, the back injection of minority carriers is strongly suppressed in comparison with conventional bipolar transistors. Furthermore, the small temperature coefficient of the current gain allows the use of these heterojunction bipolar transistors (HBT) over a wide temperature range. Most likely, the biggest advantage of such HBTs is that a better high-frequency behaviour could be obtained. However, some problems still need to be solved such as the recombination at the emitter-base interface and the high resistivity of the emitter material.On leave from University of Florida, Gainesville, Florida, USA     

ESR spectra fo matrix-isolated bromobenzene cations formed by radiolysis

Exposure of dilute solution of bromobenzene and p-dibromobenzene in fluorotrichloromethane to ⁶⁰Co_γ-rays at 77 K gave the corresponding cations characterized by ESR spectra. Estimated spin densities on bromine of ≈ 30% and 23%, respectively, are greater than those predicted by comparison with neutral α-bromo radicals, R₂CBr (≈ 15%). Evidence for dimer cation formation in more concentrated solutions is presented.     

Trapped electrons in amorphous solids: A method for estimating the concentration of molecular vacancies

The densities for n-propanol and n-butanol in their glassy and crystalline forms have been measured at 77 K. The density difference of ca. 0.11 cm³ g^?1 is comparable with that normally found between liquids and solids at their melting points. The maximum yield of trapped electrons in the γ-irradiated glassy alcohols has been estimated and, if it is assumed that they are exclusively trapped at molecular-sized vacancies present only in the glasses, then such vacancies account for no more than ca. 1.0% of the volume difference between the crystalline and glassy materials. Much of the remaining difference can be accounted for in terms of long and bent hydrogen bonds in the glasses.