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51.
Photodissociation spectra of Mg+-XCH3 (X=F, Cl, Br, and I) complexes have been measured in the ultraviolet region (225-415 nm). Several fragment ions with and without charge transfer (CT), Mg+, XCH3+, MgX+, MgCH3+, CH3+, and X+, were formed by evaporation (intermolecular bond dissociation) and intracluster reaction (intramolecular bond dissociation) via excited electronic states. Branching ratios of these ions were found to depend both on absorption bands and on halogen atoms. The ground states of the complexes were calculated to have geometries in which the Mg atom lies next to X atom of methyl halide molecules. Positive charges of the complexes are confirmed to be almost localized on Mg. Observed absorption bands were assigned to the transitions of the Mg+2P-2S atomic line perturbed by interactions with methyl halide molecules. Branching ratios of fragment ions can be partly explained by the stability of fragment ions and neutral counterparts. From the excited state potential energy curves along the Mg-X bond distance, dissociation reaction after CT was concluded to proceed predissociatively; potential curve crossings between the initially excited states and repulsive CT states may have a crucial role in the formation of CH3+, XCH3+, and X+. In particular, XCH3+ ions were formed via repulsive CT states having a character of electron excitation from Xnp to Mg+3s. 相似文献
52.
Hanada M Sugiura Y Shinjo R Masaki N Imagama S Ishiguro N Matsuyama Y Setou M 《Analytical and bioanalytical chemistry》2012,403(7):1873-1884
We determined quantitative and qualitative alterations in lipids during the occurrence and progression of spinal cord injury (SCI) in rats to identify potential clinical indicators of SCI pathology. Imaging mass spectrometry (IMS) was used to visualize twelve molecular species of phosphatidylcholine (PC) on thin slices of spinal cord with SCI. In addition, twelve species of phospholipids and five species of prostaglandins (PGs) were quantified by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) of lipid extracts from control/injured spinal cords. Unique distribution patterns were observed for phospholipids with different fatty acid compositions, and distinct dynamic changes were seen in both their amounts and their distributions in tissue as tissue damage resulting from SCI progressed. In particular, PCs containing docosahexaenoic acid localized to the large nucleus in the anterior horn region at one day post-SCI and rapidly decreased thereafter. In contrast, PCs containing arachidonic acid (AA-PCs) were normally found in the posterior horn region and were intensely and temporarily elevated one week after SCI. Lysophosphatidylcholines (LPCs) also increased at the same SCI stage and in regions with elevated AA-PCs, indicating the release of AA and the production of PGs. Moreover, LC-ESI-MS/MS analysis of lipid extracts from the spinal cord tissue at the impact site demonstrated a peak in PGE2 that reflected the elevation/reduction pattern of AA-PCs and LPC. Although further investigation is required, we suggest that invasive immune cells that penetrated from the impaired blood-brain barrier at 1-2 weeks post-SCI may have produced LPCs, released AA from AA-PCs, and produced PGs in SCI tissue at sites enriched in AA-PCs/LPC. 相似文献
53.
54.
Longitudinal sound-wave propagation has been studied in an aerogel-liquid 4He system for various porosities of aerogel. The superfluid transition was identified as the absorption peak, whose magnitude was suppressed by aerogel. The sound velocity was analyzed within a hydrodynamic theory in both normal and superfluid phases. The absorption peak due to phonon-roton interaction around 1 K was not observed even with the most porous aerogel. The low-temperature sound velocity and attenuation show that direct collisions of phonons with aerogel strands play an important role in the acoustic properties. 相似文献
55.
56.
Pavel Svoboda Pavel Javorský Fuminori Honda Vladimír Sechovský Alois A. Menovsky 《Central European Journal of Physics》2004,2(2):397-418
The tetragonal compound UNi2Si2 exhibits in zero magnetic field three different antiferromagnetic phases belowT
N
=124 K. They are formed by ferromagnetic basal planes, which are antiferromagnetically coupled along thec-axis with the propagation vectorq=(0, 0, q
z
). Two additional order-order magnetic phase transitions are observed below T
N
, namely atT
1=108 K and T
2=40 K in zero magnetic field. All three phases exhibit strong uniaxial anisotropy confining the U moments to a direction parallel
to the c-axis. UNi2Si2 single crystals were studied in detail by measuring bulk thermodynamic properties, such as thermal expansion, resistivity,
susceptibility, and specific heat. A microscopic study using neutron diffraction was performed in magnetic fields up to 14.5
T parallel to the c-axis, and a complex magnetic phase diagram has been determined. Here, we present the analysis of specific-heat data measured
in magnetic fields up to 14 T compared with the results of the neutron-diffraction study and with other thermodynamic properties
of UNi2Si2. 相似文献
57.
M. Seto Yu. Maeda T. Matsuyama H. Yamaoka H. Sakai S. Masubuchi S. Kazama K. Mizoguchi K. Kume 《Hyperfine Interactions》1992,68(1-4):217-220
The129I Mössbauer spectroscopy has been applied to iodine-doped highly conducting polyacetylene. For the unstretched polyacetylene films, the iodine species of I?, I 3 ? and I 5 ? are observed. The polyiodides have symmetrical charge population. In addition to these anions, a small amount of iodines is covalently bonding to the carbon atoms, breaking the double bonds of the main chain. For the stretched polyacetylene films, the measurements were done under the condition that the stretch direction was parallel or perpendicular to the direction of incident ψ-rays. The relative change of the intensities of the Mössbauer quadrupole-split lines reveals the alignment of the polyiodine anions in the stretched film. 相似文献
58.
59.
Hisashi Matsuyama Toshikatsu Koga Yoshihisa Kawata 《Theoretical chemistry accounts》2006,115(4):287-290
Angular correlation coefficients τ
nl,n^′ l^′ [p] between linear momenta of an electron in a subshell nl and another electron in a subshell n′ l′ are studied for the 102 neutral atoms He through Lr in their ground states, where n and l are the principal and azimuthal quantum numbers, respectively. We theoretically find that electron momenta are negatively
correlated or uncorrelated; τ
nl,n^′ l^′ [p] < 0 when |l − l′|=1, while τ
nl,n^′ l^′ [p]=0 when |l − l′| ≠ 1. Numerical examinations of the atoms show that except for the He–B atoms, negative correlations are largest between
1s and 2p subshells, which have the most diffuse electron distributions in momentum space. 相似文献
60.