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21.
Santos M de Matos AP Marçalo J Gibson JK Haire RG Tyagi R Pitzer RM 《The journal of physical chemistry. A》2006,110(17):5751-5759
Oxidation reactions of bare and ligated, monopositive, and dipositive Pa ions in the gas phase were studied by Fourier transform ion cyclotron resonance mass spectrometry. Seven oxidants were employed, ranging from the thermodynamically robust N(2)O to the relatively weak CH(2)O-all oxidized Pa(+) to PaO(+) and PaO(+) to PaO(2)(+). On the basis of experimental observations, it was established that D[Pa(+)-O] and D[OPa(+)-O] > or = 751 kJ mol(-1). Estimates for D[Pa(+)-O], D[OPa(+)-O], IE[PaO], and IE[PaO(2)] were also obtained. The seven oxidants reacted with Pa(2+) to produce PaO(2+), indicating that D[Pa(2+)-O] > or = 751 kJ mol(-1). A particularly notable finding was the oxidation of PaO(2+) by N(2)O to PaO(2)(2+), a species, which formally comprises Pa(VI). Collision-induced dissociation of PaO(2)(2+) suggested the protactinyl connectivity, {O-Pa-O}(2+). The experimentally determined IE[PaO(2)(+)] approximately 16.6 eV is in agreement with self-consistent-field and configuration interaction calculations for PaO(2)(+) and PaO(2)(2+). These calculations provide insights into the electronic structures of these ions and indicate the participation of 5f orbitals in bonding and a partial "6p hole" in the case of protactinyl. It was found that PaO(2)(2+) catalyzes the oxidation of CO by N(2)O-such O atom transport via a dipositive metal oxide ion is distinctive. It was also observed that PaO(2)(2+) is capable of activating H(2) to form the stable PaO(2)H(2+) ion. 相似文献
22.
Single and two-photon excited emission has been observed from a curiumdoped borosilicate glass matrix at both room and liquid nitrogen temperatures. The emission spectrum was measured using several different excitation energies and intensities. In addition to the expected line narrowing, variations in the ratios of emission intensities between states, and between crystal field levels within the each state were observed with cooling. Slight variations in the emission spectrum also arose as a function of the excitation intensity. These variations in the Cm ion's emission spectrum as a function of experimental parameters are presented and discussed. 相似文献
23.
H. Backe A. Dretzke St. Fritzsche R. G. Haire P. Kunz W. Lauth M. Sewtz N. Trautmann 《Hyperfine Interactions》2005,162(1-4):3-14
The level scheme and hyperfine structure of the element fermium (Z = 100) has been investigated with the method of resonance ionization spectroscopy in a buffer gas cell. The experiments were
carried out on a 46 pg sample of the isotope 255Fm with a half-life time of 20.1 h, produced in the high flux nuclear reactor of the ORNL, Oak Ridge, USA. A wave number scan
from 27,100 to 28,400 cm−1 was carried through to search for three levels with large Einstein-coefficients, as predicted by ab initio Multi-Configuration-Dirac-Fock (MCDF) calculations, and five new levels were found. In addition, the two known levels at
wave numbers (25,099.8 ± 0.2) and (25,111.8 ± 0.2) cm−1 were studied with a laser band width of 1.5 GHz and hyperfine broadenings were observed. 相似文献
24.
Conradson SD Abney KD Begg BD Brady ED Clark DL den Auwer C Ding M Dorhout PK Espinosa-Faller FJ Gordon PL Haire RG Hess NJ Hess RF Keogh DW Lander GH Lupinetti AJ Morales LA Neu MP Palmer PD Paviet-Hartmann P Reilly SD Runde WH Tait CD Veirs DK Wastin F 《Inorganic chemistry》2004,43(1):116-131
Pu L(3) X-ray near edge absorption spectra for Pu(0-VII) are reported for more than 60 chalcogenides, chlorides, hydrates, hydroxides, nitrates, carbonates, oxy-hydroxides, and other compounds both as solids and in solution, and substituted in zirconolite, perovskite, and borosilicate glass. This large database extends the known correlations between the energy and shape of these spectra from the usual association of the XANES with valence and site symmetry to higher order chemical effects. Because of the large number of compounds of these different types, a number of novel and unexpected behaviors are observed, such as effects resulting from the medium and disorder that can be as large as those from valence. 相似文献
25.
Black crystals of Np(PS(4)), Np(P(2)S(6))(2), K(11)Np(7)(PS(4))(13), and Rb(11)Np(7)(PS(4))(13) have been synthesized by the reactions of Np, P(2)S(5), and S at 1173 and 973 K; Np, K(2)S, P, and S at 773 K; and Np, Rb(2)S(3), P, and S at 823 K, respectively. The structures of these compounds have been characterized by single-crystal X-ray diffraction methods. Np(PS(4)) adopts a three-dimensional structure with Np atoms coordinated to eight S atoms from four bidentate PS(4)(3-) ligands in a distorted square antiprismatic arrangement. Np(PS(4)) is isostructural to Ln(PS(4)) (Ln = La-Nd, Sm, Gd-Er). The structure of Np(P(2)S(6))(2) is constructed from three interpenetrating diamond-type frameworks with Np atoms coordinated to eight S atoms from four bidentate P(2)S(6)(2-) ligands in a distorted square antiprismatic geometry. The centrosymmetric P(2)S(6)(2-) anion comprises two PS(2) groups connected by two bridging S centers. Np(P(2)S(6))(2) is isostructural to U(P(2)S(6))(2). A(11)Np(7)(PS(4))(13) (A = K, Rb) adopts a three-dimensional channel structure built from interlocking [Np(7)(PS(4))(13)](11-)-screw helices with A cations residing in the channels. The structure of A(11)Np(7)(PS(4))(13) includes four crystallographically independent Np atoms. Three are connected to eight S atoms in bicapped trigonal prisms. The other Np atom is connected to nine S atoms in a tricapped trigonal prism. A(11)Np(7)(PS(4))(13) is isostructural to A(11)U(7)(PS(4))(13). From Np-S bond distances and charge-balance, we infer that Np is trivalent in Np(PS(4)) and tetravalent in Np(P(2)S(6))(2) and A(11)Np(7)(PS(4))(13). Np exhibits a behavior intermediate between U and Pu in its thiophosphate chemistry. 相似文献
26.
Black prisms of Np(3)Q(5) (Q = S, Se) have been synthesized by the stoichiometric reactions between Np and Q at 1173 K in a CsCl flux. The structures of these compounds were characterized by single-crystal X-ray diffraction methods. The Np(3)Q(5) compounds are isostructural with U(3)Q(5). The structure of Np(3)Q(5) is constructed from layers of Np(1)Q(8) distorted bicapped trigonal prisms that share faces with each other on bc planes. Each Np(1)Q(8) layer further shares Q(2) edges with two adjacent identical neighbors to form a three-dimensional framework. The space inside each channel within this framework is filled by one single edge-sharing Np(2)Q(7) distorted 7-octahedron chain running along the b axis. Magnetic susceptibility measurements show that Np(3)S(5) and Np(3)Se(5) have antiferromagnetic orderings at 35(1) and 36(1) K, respectively. Above the magnetic ordering temperatures, both Np(3)S(5) and Np(3)Se(5) behave as typical Curie-Weiss paramagnets. The effective moments obtained from the fit of the magnetic data to a modified Curie-Weiss law over the temperature range 70 to 300 K are 2.7(2) μ(B) (Np(3)S(5)) and 2.9(2) μ(B) (Np(3)Se(5)). 相似文献
27.
Abstract Luminescence spectra from Eu3+ ion in C-type Eu2O3 under high pressures have been obtained. The spectral shifts can be used to study the effect of pressure on the spin-orbit and the Coulomb interactions of the 4f electrons, which are correlated with expansion of the 4f-electron wave functions. This expansion with the application of pressure results in both the variation of the electronegativity and radius of the Eu3+ ion and, ultimately, the phase transformation from C-to B-type Eu2O3. Therefore, core 4f-electrons can thus be thought of as quasivalence electrons. 相似文献
28.
Antoniazzi L Arenton M Cao Z Chen T Conetti S Corti G Cox B Delchamps S Fortney L Guffey K Haire M Ioannou P Jenkins CM Judd DJ Kourkoumelis C Manousakis-Katsikakis A Kuzminski J LeCompte T Marchionni A He M Mazur PO Murphy CT Pramantiotis P Rameika R Resvanis LK Rosati M Rosen J Shen C Shen Q Simard A Smith RP Spiegel L Stairs DG Tan Y Tesarek RJ Turkington T Turnbull L Turkot F Tzamarias S Voulgaris G Wagoner DE Wang C Yang W Yao N Zhang N Zhang X Zioulas G Zou B 《Physical review D: Particles and fields》1994,50(7):4258-4264
29.