Individual solvation numbers around the nickel(II) ion in an N,N-dimethylformamide and N,N-dimethylacetamide mixture determined by Raman spectrophotometry.

Individual solvation numbers around the nickel(II) ion have been determined by titration Raman spectroscopy in N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) mixtures at 298 K. The in-plane bending vibration (delta(O=C-N)) of DMF and the stretching vibration (v(N-CH3)) of DMA were used in the present analysis. These Raman bands of solvent molecules shift to higher frequencies upon coordination of the solvent molecules to the metal ion. By analyzing the band intensities of free and bound solvent molecules with increasing concentration of the metal ion, the solvation number around the metal ion can be evaluated. Because the individual solvation numbers of DMF and DMA around the nickel(II) ion in the mixture are determined independently, the total solvation number is obtained as their sum. It was found that the total solvation number remains 6 in all mixtures of the DMA mole fraction x = 0 - 1. Although DMF and DMA have practically the same electron-pair donor capacities, the nickel(II) ion prefers DMF to DMA, and an equal solvation number is attained at x = 0.75. This is ascribed to the solvation steric effect of DMA.     

Copolymerization of styrene and conjugated dienes with half‐sandwich titanium(IV) catalysts: The effect of the ligand structure on the monomer reactivity,monomer sequence distribution,and insertion mode of dienes

The copolymerization of styrene and 1,3‐butadiene (Bd) or isoprene (Ip) was carried out with half‐sandwich titanium(IV) Cp′TiCl₃ catalysts (where Cp′ is cyclopentadienyl 1 , indenyl 2 , or pentamethylcyclopentadienyl 3 ) with methylaluminoxane as a cocatalyst. For the copolymerization with Bd, catalyst 3 gave the copolymers containing the highest amount of Bd among the catalysts used. The resulting copolymers were composed of a styrene–Bd multiblock sequence. High melting points were observed in the copolymers prepared with catalyst 1 . The structures of hydrogenated poly(styrene‐co‐Bd) were studied by ¹³C NMR spectroscopy, and the long styrene sequence length was detected in the copolymers prepared with catalyst 1 . For styrene/Ip copolymerization, random copolymers were obtained. Among the used catalysts, catalyst 1 gave the copolymers containing the highest amount of Ip. The copolymers prepared with catalyst 1 showed a steep melting point depression with increasing Ip content because of the high ratio of 1,4‐inserted Ip units and/or the low molecular weights of the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 939–946, 2003     

Experimental evidences for molecular origin of low-Q peak in neutron/x-ray scattering of 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ionic liquids

Short- and long-range liquid structures of [C(n)mIm(+)][TFSA(-)] with n = 2, 4, 6, 8, 10, and 12 have been studied by high-energy x-ray diffraction (HEXRD) and small-angle neutron scattering (SANS) experiments with the aid of MD simulations. Observed x-ray structure factor, S(Q), for the ionic liquids with the alkyl-chain length n > 6 exhibited a characteristic peak in the low-Q range of 0.2-0.4 A?(-1), indicating the heterogeneity of their ionic liquids. SANS profiles I(H)(Q) and I(D)(Q) for the normal and the alkyl group deuterated ionic liquids, respectively, showed significant peaks for n = 10 and 12 without no form factor component for large spherical or spheroidal aggregates like micelles in solution. The peaks for n = 10 and 12 evidently disappeared in the difference SANS profiles ΔI(Q) [=I(D)(Q) - I(H)(Q)], although that for n = 12 slightly remained. This suggests that the long-range correlations originated from the alkyl groups hardly contribute to the low-Q peak intensity in SANS. To reveal molecular origin of the low-Q peak, we introduce here a new function; x-ray structure factor intensity at a given Q as a function of r, S(Q) (peak)(r). The S(Q) (peak)(r) function suggests that the observed low-Q peak intensity depending on n is originated from liquid structures at two r-region of 5-8 and 8-15 A? for all ionic liquids examined except for n = 12. Atomistic MD simulations are consistent with the HEXRD and SANS experiments, and then we discussed the relationship between both variations of low-Q peak and real-space structure with lengthening the alkyl group of the C(n)mIm.     

Geometrical structure of benzene and naphthalene: ultrahigh-resolution laser spectroscopy and ab initio calculation

Geometrical structures of the isolated benzene and naphthalene molecules have been accurately determined by using ultrahigh-resolution laser spectroscopy and ab initio calculation in a complementary manner. The benzene molecule has been identified to be planar and hexagonal (D(6h)) and the structure has been determined with accuracies of 2 × 10(-14) m (0.2 mA?; 1 A? = 1 × 10(-10) m) for the C-C bond length and 1.0 × 10(-13) m (1.0 mA?) for the C-H bond length. The naphthalene molecule has been identified to be symmetric with respect to three coordinate axes (D(2h)) and the structure has been determined with comparable accuracies. We discuss the effect of vibrational averaging that is a consequence of zero-point motions on the uncertainty in determining the bond lengths.     

Magnetic properties and magnetic structures of Sr3−xCaxRu2O7

We have measured magnetization curves and powder neutron diffraction of double-layered Ruddlesden-Popper type ruthenate Sr_3−xCa_xRu₂O₇ (x=1.5, 2.0 and 3.0). The field dependence of the magnetization revealed that the transition field of metamagnetic transition along the b-axis shifted to lower fields and that the transition became broad with increasing Sr content. The slope of the magnetization curve also increased with increasing Sr content below the metamagnetic transition. These results indicate that an itinerant component is partly introduced by the Sr substitution. From the magnetic reflection, on cooling below T_N, an additional reflection was observed at (0 0 1) for each x, and the amplitude increased with decreasing temperature. The observed diffraction patterns are very similar to those of Ca₃Ru₂O₇. We conclude that the magnetic structure of the antiferromagnetic ordered phase is basically the same structure with that of Ca₃Ru₂O₇.     

Feasibility study of the standing accretion shock instability experiment at the National Ignition Facility

The primary hydrodynamic flow feature of early explosion phases of a core-collapse supernova is a spherical shock. This shock is born deep in the central regions of the collapsing stellar core, stalls shortly afterward, and in case of a successful explosion is revived and becomes the supernova shock. The revival process involves a standing accretion shock instability, SASI. This shock instability is considered the key processes aiding the core-collapse supernova (ccSN) explosion.The aim of our study is to identify feasible conditions and parameters for an experimental system that is able to capture the essential characteristics of SASI. We use semi-analytic methods and high-resolution hydrodynamic simulations in multidimensions to investigate a possible experimental design on the National Ignition Facility. The experimental configuration involves a steady, spherical shock. We explore a viable region of parameters and obtain limits on the shocked flow geometry. We study the stability properties of the shock and its post-shock region.We compare properties of the experimental design and the ccSN environment. The obtained model experimental flow field closely resembles converging nozzle flow. The post-shock region, in contrast to the supernova setting, is found to be stably stratified and stable against to perturbations upstream of the shock. We conclude that it is not possible to capture the characteristics of the ccSN SASI for the converging shocked flow configuration considered here. However, such configuration offers a very stable setting for precision studies of dense, high-temperature plasmas requiring finely-controlled conditions and long lifetimes.     

Suppression of the Rayleigh-Taylor instability due to self-radiation in a multiablation target

A scheme to suppress the Rayleigh-Taylor instability has been investigated for a direct-drive inertial fusion target. In a high-Z doped-plastic target, two ablation surfaces are formed separately-one driven by thermal radiation and the other driven by electron conduction. The growth of the Rayleigh-Taylor instability is significantly suppressed on the radiation-driven ablation surface inside the target due to the large ablation velocity and long density scale length. A significant reduction of the growth rate was observed in simulations and experiments using a brominated plastic target. A new direct-drive pellet was designed using this scheme.     

Small hyperintense hepatic lesions on T1-weighted images in patients with cirrhosis: evaluation with serial MRI and imaging features for clinical benignity

PURPOSE: The aim of this study was to evaluate the frequency and magnetic resonance imaging (MRI) features of clinically benign, small (<2 cm) hyperintense hepatic lesions in the cirrhotic liver on T1-weighted MR images seen at serial MRI. MATERIALS AND METHODS: This study included 189 patients with cirrhosis, who underwent hepatic MRI more than twice with an interval of at least 12 months. The initial MR images were reviewed for the presence of small hyperintense lesions on T1-weighted images. The size, location and signal intensity on T2-weighted images as well as enhancement patterns of the corresponding lesions were recorded. RESULTS: On the initial T1-weighted MR images, 43 small hyperintense hepatic lesions were detected in 23 (12%) of 189 patients. Twelve (28%) of 43 lesions showed early enhancement and were pathologically diagnosed as hepatocellular carcinoma (HCC) during the follow-up period. Thirty-one (72%) of 43 lesions showed no early enhancement with various signal intensity on T2-weighted images (hyperintensity=4, isointensity=20, hypointensity=7). Among these 31 lesions, 12 showed no interval change, while 11 disappeared (n=10) or decreased in size (n=1). In the remaining eight lesions, seven were diagnosed as HCC on the basis of pathologic confirmation or the interval growth. CONCLUSION: Small hyperintense hepatic lesions on T1-weighted magnetic resonance (MR) images without early enhancement on the arterial-phase contrast-enhanced dynamic studies in patients with cirrhosis usually showed no interval growth or disappeared during the serial MRI. These lesions with additional findings of iso- or hypointensity on the T2-weighted MR images without "washout effect" on the contrast-enhanced equilibrium-phase images may more frequently be clinically benign or hyperplastic nodules than HCCs.     

Anion conformation of low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide

Anion conformation of a low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide (EMI+FSI-) has been studied by Raman spectra and theoretical DFT calculations. Three strong Raman bands were found at 293, 328, and 360 cm(-1), which are ascribed to the FSI- ion. These Raman bands show significant temperature dependence, implying that two FSI- conformers coexist in equilibrium. This is supported by theoretical calculations that the FSI- ion is present as either C2 (trans) or C1 (cis) conformer; the former gives the global minimum, and the latter has a higher SCF energy of about 4 kJ mol(-1). Full geometry optimizations followed by normal frequency analyses show that the observed bands at 293, 328, and 360 cm(-1) are ascribed to the C2 conformer. The corresponding vibrations at 305, 320, and 353 cm(-1) were extracted according to deconvolution of the observed Raman bands in the range280-400 cm(-1 )and are ascribed to the C1 conformer. The enthalpy DeltaH degrees of conformational change from C2 to C1 was experimentally evaluated to be ca. 4.5 kJ mol(-1), which is in good agreement with the predicted value by theoretical calculations. The bis(trifluoromethanesulfonyl) imide anion (TFSI-) shows a conformational equilibrium between C1 and C2 analogues (DeltaH degrees = 3.5 kJ mol(-1)). However, the profile of the potential energy surface of the conformational change for FSI- (the F-S-N-S dihedral angle) is significantly different from that for TFSI- (the C-S-N-S dihedral angle).     

Ab initio molecular orbital study of dications of 1,5‐dichalcogenacyclooctanes

The molecular and electronic structures of the dications of three homonuclear and three heteronuclear dichalcogenacyclooctanes (chalcogen = S, Se, or Te) were investigated by ab initio molecular orbital calculations. Four energy‐minimum structures were located for each dication. Three of those (chair‐chair, boat‐boat, and boat‐chair) have the cis configuration with respect to the chalcogen lone pairs, and the remaining one has the trans configuration. The cis isomers were found to be much more stable than the trans isomer. Among the three cis structures, the stability is in the order of boat‐chair > boat‐boat > chair‐chair for all dications. This order can be explained by considering the nonbonding H···H interactions. The chair‐chair structure (C_2v symmetry) of the 1,5‐dithiacyclooctane dication has a very low vibrational frequency of a₂ symmetry, and its LUMO energy is lower than those of boat‐boat and boat‐chair. These can rationalize the fact that in the crystalline state the dication adopts a distorted C₂ chair‐chair conformation. The transition states between the three conformers of the homonuclear dications were also located. The corresponding energy barriers are relatively low, which is consistent with their NMR spectra. The relative stabilities of the homonuclear and heteronuclear dications were elucidated on the basis of their energies and those of the corresponding neutral compounds. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:31–41, 2000