Numerical Simulation Studies of the Long-term Evolution of a CO<Subscript>2</Subscript> Plume in a Saline Aquifer with a Sloping Caprock

We have used the TOUGH2-MP/ECO2N code to perform numerical simulation studies of the long-term behavior of CO₂ stored in an aquifer with a sloping caprock. This problem is of great practical interest, and is very challenging due to the importance of multi-scale processes. We find that the mechanism of plume advance is different from what is seen in a forced immiscible displacement, such as gas injection into a water-saturated medium. Instead of pushing the water forward, the plume advances because the vertical pressure gradients within the plume are smaller than hydrostatic, causing the groundwater column to collapse ahead of the plume tip. Increased resistance to vertical flow of aqueous phase in anisotropic media leads to reduced speed of up-dip plume advancement. Vertical equilibrium models that ignore effects of vertical flow will overpredict the speed of plume advancement. The CO₂ plume becomes thinner as it advances, but the speed of advancement remains constant over the entire simulation period of up to 400 years, with migration distances of more than 80 km. Our simulations include dissolution of CO₂ into the aqueous phase and associated density increase, and molecular diffusion. However, no convection develops in the aqueous phase because it is suppressed by the relatively coarse (sub-) horizontal gridding required in a regional-scale model. A first crude sub-grid-scale model was developed to represent convective enhancement of CO₂ dissolution. This process is found to greatly reduce the thickness of the CO₂ plume, but, for the parameters used in our simulations, does not affect the speed of plume advancement.     

Open Chain Chiral Macrolide Building Blocks by Opening of Deoxygenated 1,6-Anhydrosugars with 1,3-Propanedithiol

Chiral building blocks for macrolides and related natural products are obtained from 1,6-anhydrosugars by conversion of the bicyclic acetals 2 or 12 into the open chain chiral 1,3-dithianes 6 and 13. Branched precursors can be obtained by opening of the ?erný epoxide 1 with the 1,3-dithiane anion to yield 7, followed by ring opening with 1,3-propanedithiol to the bis-1,3-dithiane 8.     

Thin Film Counterelectrodes with High Li Charge Capacity for Electrochromic Windows

Summary.  Ce-V mixed oxide films have been deposited by RF sputtering with the aim of increasing the Li charge capacity of counter electrodes in smart windows. Such mixed oxides have shown high transmittance and optical passivity in the visible region. After electrode pre-conditioning by cyclic voltammetry, a good electrochemical reversibility in LiClO₄– propylene carbonate electrolyte was observed, and large Li-charge capacity under galvanostatic charging (up to 50 mCċcm⁻²) has been measured. The electrode charge capacity decreased after prolonged insertion-deinsertion cycles, whereas the photoptic transmittance remained about constant. After 800 cycles the Li-charge capacity decreased to 40 mCċcm⁻². The Li diffusion coefficient inside the films measured by electrochemical impedance and by galvanostatic titration ranged from 10⁻¹¹ cm²ċs⁻¹ to 10⁻¹³cm²ċs⁻¹. We observed that the Li charge capacity of the film electrodes is a function of the film deposition conditions, because it increased with the vanadium oxide concentration in the target and with the oxygen content in the sputtering atmosphere. Received June 23, 2000. Accepted (revised) August 7, 2000     

Global G-Manifold Reductions and Resolutions

The purpose of this note is to exhibit some simple and basic constructions for smooth compact transformation groups, and some of their most immediate applications to geometry.     

Applying Unconventional Spectroscopies to the Single-Molecule Magnets,Co(PPh3)2X2 (X=Cl,Br, I): Unveiling Magnetic Transitions and Spin-Phonon Coupling

Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging. We have found that far-IR magnetic spectra (FIRMS) of Co(PPh₃)₂X₂ ( Co-X ; X=Cl, Br, I) reveal rarely observed spin-phonon coupling as avoided crossings between magnetic and u-symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero-field split (ZFS) levels of the S=3/2 electronic ground state were probed by INS, high-frequency and -field EPR (HFEPR), FIRMS, and frequency-domain FT terahertz EPR (FD-FT THz-EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) and g values. Ligand-field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities in Co-X , showing that the larger Co(II) spin density in a molecule, the larger its ZFS magnitude. The current work reveals dynamics of magnetic and phonon excitations in SMMs. Studies of such couplings in the future would help to understand how spin-phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling.