^(18)O/^(16)O and D/H studies on the interactions between heated meteoric ground waters and igneous intrusions: Western San Juan Mountains, Colorado and the Isle of Skye, Scotland

Detailed oxygen, hydrogen and carbon isotope studies have been carried out on igneous and metamorphic rocks of the Stony Mountain complex, Colorado, and the Isle of Skye, Scotland, in order to better understand the problems of hydrothermal meteoric water-rock interaction.

The Tertiary Stony Mountain stock (~1.3 km in diameter), is composed of an outer diorite, a main mass of biotite gabbro, and an inner diorite. The entire complex and most of the surrounding country rocks have experienced various degrees of ¹⁸O depletion (up to 10 per mil) due to interaction with heated meteoric waters. The inner diorite apparently formed from a low-¹⁸O magma with δ¹⁸O ≃ +2.5, but most of the isotopic effects are a result of exchange between H₂O and solidified igneous rocks. The low-¹⁸O inner diorite magma was probably produced by massive assimilation and/or melting of hydrothermally altered country rocks. The δ¹⁸O values of the rocks generally increase with increasing grain size, except that quartz typically has δ¹⁸O = +6 to +8, and is more resistant to hydrothermal exchange than any other mineral studied. Based on atom % oxygen, the outer diorites, gabbros, and volcanic rocks exhibit integrated water/rock ratios of 0.3 ± 0.2, 0.15 ± 0.1, and 0.2 ± 0.1, respectively. Locally, water/rock ratios attain values greater than 1.0. Hydrogen isotopic analyses of sericites, chlorites, biotites, and amphiboles range from -117 to -150. δD in biotites varies inversely with Fe/Fe+Mg, as predicted by Suzuoki and Epstein (1974), and positively with elevation, over a range of 600 m. The calculated δD of the mid-to-late-Tertiary meteoric waters is about -100. Carbonate δ¹³C values average -5.5 (PDB), within the generally accepted range for deep-seated carbon.

Almost all the rocks within 4 km of the central Tertiary intrusive complex of Skye are depleted in ¹⁸O. Whole-rock δ¹⁸O values of basalts (-7. 1 to +8.4), Mesozoic shales (-0.6 to + 12.4), and Precambrian sandstones (-6.2 to + 10.8) systematically decrease inward towards the center of the complex. The Cuillin gabbro may have formed from a ¹⁸O-depleted magma (depleted by about 2 per mil); δ¹⁸O of plagioclase (-7.1 to + 2.5) and pyroxene (-0.5 to + 3.2) decrease outward toward the margins of the pluton. The Red Hills epigranite plutons have δ¹⁸O quartz (-2.7 to + 7.6) and feldspar (-6.7 to + 6.0) that suggest about 3/4 of the exchange took place at subsolidus temperatures; profound disequilibrium quartz-feldspar fractionations (up to 12) are characteristic. The early epigranites were intruded as low-¹⁸O melts (depletions of up to 3 per mil) with δ¹⁸O of the primary, igneous quartz decreasing progressively with time. The Southern Porphyritic Epigranite was apparently intruded as a low-¹⁸O magma with δ¹⁸O ≃ -2.6. A good correlation exists between grain size and δ¹⁸O for the unique, high-¹⁸O Beinn an Dubhaich granite which intrudes limestone having a δ¹⁸O range of +0.5 to +20.8, and δ¹³C of -4.9 to -1.0. The δD values of sericites (-104 to -107), and amphiboles, chlorites, and biotites (-105 to -128) from the igneous rocks , indicate that Eocene surface waters at Skye had δD ≃ -90. The average water/rock ratio for the Skye hydrothermal system is approximately one; at least 2000 km³ of heated meteoric waters were cycled through these rocks.

Thus these detailed isotopic studies of two widely separated areas indicate that (1) ¹⁸O-depleted magmas are commonly produced in volcanic terranes invaded by epizonal intrusions; (2) most of the ¹⁸O-depletion in such areas are a result of subsolidus exchange (particularly of feldspars); however correlation of δ¹⁸O with grain size is generally preserved only for systems that have undergone relatively minor meteoric hydrothermal exchange; (3) feldspar and calcite are the minerals mos t susceptible to oxygen isotopic exchange, whereas quartz is very resistant to oxygen isotope exchange; biotite, magnetite, and pyroxene have intermediate susceptibilities; and (4) basaltic country rocks are much more permeable to the hydrothermal convective system than shale, sandstone, or the crystalline basement complex.

Neutron-neutron scattering parameters from the ^3He(d,t)2p and ^3H(d,^3He)2n reactions

The energy spectra of tritons and Helium-3 nuclei from the reactions ³He(d,t)2p, ³H(d,³He)2n, ³He(d,³He)pn, and ³H(d,t)pn were measured between 6° and 20° at a bombarding energy of 10.9 MeV. An upper limit of 5 μb/sr. was obtained for producing a bound di-neutron at 6° and 7.5°. The ³He(d,t)2p and ³H(d,³He)2n data, together with previous measurements at higher energies, have been used to investigate whether one can unambiguously extract information on the two-nucleon system from these three-body final state reactions. As an aid to these theoretical investigations, Born approximation calculations were made employing realistic nucleon-nucleon potentials and an antisymmetrized final state wave function for the five-particle system. These calculations reproduce many of the features observed in the experimental data and indicate that the role of exchange processes cannot be ignored. The results show that previous attempts to obtain information on the neutron-neutron scattering length from the ³H(d,³He)2n reaction may have seriously overestimated the precision that could be attained.

I. Configurational stability and redistribution equilibria in organomagnesium compounds. II. Redistribution equilibria in organocadmium compounds

I. CONFIGURATIONAL STABILITY AND REDISTRIBUTION EQUILIBRIA IN ORGANOMAGNESIUM COMPOUNDS

The dependence of the rate of inversion of a dialkylmagnesium compound on the solvent has been studied.

Examination of the temperature dependence of the nuclear magnetic resonance spectrum of 1-phenyl-2-propylmagnesium bromide in diethyl ether solution indicates that inversion of configuration at the methylene group of this Grignard reagent occurs with an approximate rate of 2 sec^-1 at room temperature. This is the first example of a rapid inversion rate in a secondary Grignard reagent.

The rates of exchange of alkyl groups between dineopentylmagnesium and di-s-butylmagnesium, bis-(2-methylbutyl)-magnesium and bis-(4, 4-dimethyl-2-pentyl)-magnesium respectively in diethyl ether solution were found to be fast on the nmr time scale. However, the alkyl group exchange rate was found to be slow in a diethyl ether solution of dineopentylmagnesium and bis-(2-methylbutyl)-magnesium containing N, N, N', N'-tetramethylethylenediamine. The unsymmetrical species neopentyl-2-methylbutyl-magnesium was observed at room temperature in the nmr spectrum of the solution containing the diamine.

II. REDISTRIBUTION EQUILIBRIA IN ORGANOCADMIUM COMPOUNDS

The exchange of methyl groups in dimethylcadmium has been studied by nuclear magnetic resonance spectroscopy. Activation parameters for the methyl group exchange have been measured for a neat sample and for a solution in tetrahydrofuran. The exchange is faster in the basic solvent tetrahydrofuran relative to the neat sample and in tetrahydrofuran solution is retarded by the solvating agent N, N, N’, N’-tetramethylethylenediamine and greatly increased by cadmium bromide. The addition of methanol to a solution of dimethylcadmium in tetrahydrofuran appears to have very little effect on the rate of exchange. The exchange was found to proceed with retention of configuration. The rate-limiting step for the exchange of methyl groups in a basic solvent appears to be the dissociation of coordinating solvent from dimethylcadmium.

The equilibrium between methylcadmium bromide, dimethylcadmium and cadmium bromide in tetrahydrofuran solution has also been studied. At room temperature the interconversion of the species is very fast on the nmr time scale but at -100° distinct absorptions for methylcadmium bromide and imethylcadmium are observed.

The species ethylmethylcadmium has been observed in the nmr spectrum.

The rate of exchange of vinyl groups in a solution of divinylcadmium in tetrahydrofuran has been found to be fast on the nmr time scale.

Spin wave resonance in ferromagnetic films

The objective of this investigation has been a theoretical and experimental understanding of ferromagnetic resonance phenomena in ferromagnetic thin films, and a consequent understanding of several important physical properties of these films. Significant results have been obtained by ferromagnetic resonance, hysteresis, torque magnetometer, He ion backscattering, and X-ray fluorescence measurements for nickel-iron alloy films.

Taking into account all relevant magnetic fields, including the applied, demagnetizing, effective anisotropy and exchange fields, the spin wave resonance condition applicable to the thin film geometry is presented. On the basis of the simple exchange interaction model it is concluded that the normal resonance modes of an ideal film are expected to be unpinned. The possibility of nonideality near the surface of a real film was considered by means of surface anisotropy field, inhomogeneity in demagnetizing field and inhomogeneity of magnetization models. Numerical results obtained for reasonable parameters in all cases show that they negligibly perturb the resonance fields and the higher order mode shapes from those of the unpinned modes of ideal films for thicknesses greater than 1000 Å. On the other hand for films thinner than 1000 Å the resonance field deviations can be significant even though the modes are very nearly unpinned. A previously unnoticed but important feature of all three models is that the interpretation of the first resonance mode as the uniform mode of an ideal film allows an accurate measurement of the average effective demagnetizing field over the film volume. Furthermore, it is demonstrated that it is possible to choose parameters which give indistinguishable predictions for all three models, making it difficult to uniquely ascertain the source of spin pinning in real films from resonance measurements alone.

Spin wave resonance measurements of 81% Ni-19% Fe coevaporated films 30 to 9000 Å thick, at frequencies from 1 to 8 GHz, at room temperature, and with the static magnetic field parallel and perpendicular to the film plane have been performed. A self-consistent analysis of the results for films thicker than 1000 Å, in which multiple excitations can be observed, shows for the first time that a unique value of exchange constant A can only be obtained by the use of unpinned mode assignments. This evidence and the resonance behavior of films thinner than 1000 Å strongly imply that the magnetization at the surfaces of permalloy films is very weakly pinned. However, resonance measurements alone cannot determine whether this pinning is due to a surface anisotropy, an inhomogeneous demagnetizing field or an inhomogeneous magnetization. The above analysis yields a value of 4πM=10,100 Oe and A = (1.03 ± .05) x 10^-6 erg/cm for this alloy. The ability to obtain a unique value of A suggests that spin wave resonance can be used to accurately characterize the exchange interaction in a ferromagnet.

In an effort to resolve the ambiguity of the source of pinning of the magnetization, a correlation of the ratio of magnetic moment and X-ray film thickness with the value of effective demagnetizing field 4πNM as determined from resonance, for films 45 to 300 Å has been performed. The remarkable agreement of both quantities and a comparison with the predictions of five distinct models, strongly imply that the thickness dependence of both quantities is related to a thickness dependent average saturation magnetization, which is far below 10,100 Oe for very thin films. However, a series of complementary experiments shows that this large decrease of average saturation magnetization cannot be simply explained by either oxidation or interdiffusion processes. It can only be satisfactorily explained by an intrinsic decrease of the average saturation magnetization for very thin films, an effect which cannot be justified by any simple physical considerations.

Recognizing that this decrease of average saturation magnetization could be due to an oxidation process, a correlation of resonance measurements, He ion backscattering, X-ray fluorescence and torque magnetometer measurements, for films 40 to 3500 Å thick has been performed. On basis of these measurements it is unambiguously established that the oxide layer on the surface of purposefully oxidized 81% Ni-19% Fe evaporated films is predominantly Fe-oxide, and that in the oxidation process Fe atoms are removed from the bulk of the film to depths of thousands of angstroms. Extrapolation of results for pure Fe films indicates that the oxide is most likely α-Fe₂O₃. These conclusions are in agreement with results from old metallurgical studies of high temperature oxidation of bulk Fe and Ni-Fe alloys. However, X-ray fluorescence results for films oxidized at room temperature, show that although the preferential oxidation of Fe also takes place in these films, the extent of this process is by far too small to explain the large variation of their average saturation magnetization with film thickness.

Theory of s-d exchange scattering in dilute magnetic alloys

The problem of s-d exchange scattering of conduction electrons off localized magnetic moments in dilute magnetic alloys is considered employing formal methods of quantum field theoretical scattering. It is shown that such a treatment not only allows for the first time, the inclusion of multiparticle intermediate states in single particle scattering equations but also results in extremely simple and straight forward mathematical analysis. These equations are proved to be exact in the thermodynamic limit. A self-consistent integral equation for electron self energy is derived and approximately solved. The ground state and physical parameters of dilute magnetic alloys are discussed in terms of the theoretical results. Within the approximation of single particle intermediate states our results reduce to earlier versions. The following additional features are found as a consequence of the inclusion of multiparticle intermediate states;

(i) A non analytic binding energy is pre sent for both, antiferromagnetic (J < o) and ferromagnetic (J > o) couplings of the electron plus impurity system.

(ii) The correct behavior of the energy difference of the conduction electron plus impurity system and the free electron system is found which is free of unphysical singularities present in earlier versions of the theories.

(iii) The ground state of the conduction electron plus impurity system is shown to be a many-body condensate state for J < o and J > o, both. However, a distinction is made between the usual terminology of "Singlet" and "Triplet" ground states and nature of our ground state.

(iv) It is shown that a long range ordering, leading to an ordering of the magnetic moments can result from a contact interaction such as the s-d exchange interaction.

(v) The explicit dependence of the excess specific heat of the Kondo systems is obtained and found to be linear in temperatures as T→ o and T ℓnT for 0.3 T_K ≤ T ≤ 0.6 T_K. A rise in (ΔC/T) for temperatures in the region 0 < T ≤ 0.1 T_K is predicted. These results are found to be in excellent agreement with experiments.

(vi) The existence of a critical temperature for Ferromagnetic coupling (J > o) is shown. On the basis of this the apparent contradiction of the simultaneous existence of giant moments and Kondo effect is resolved.

Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.