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1.
High‐pressure modifications of the rare earth oxide fluorides REOF (RE = Pr, Nd, Sm – Gd) were successfully synthesized under conditions of 11 GPa and 1200 °C applying the multianvil high‐pressure/high‐temperature technique. Single crystals of HP‐REOF (RE = Nd, Sm, Eu) were obtained making it possible to analyze the products by means of single‐crystal X‐ray diffraction. The compounds HP‐REOF (RE = Nd, Sm, Eu) crystallize in the orthorhombic α‐PbCl2‐type structure (space group Pnma, No. 62, Z = 4) with the parameters a = 632.45(3), b = 381.87(2), c = 699.21(3) pm, V = 0.16887(2) nm3, R1 = 0.0156, and wR2 = 0.0382 for HP‐NdOF, a = 624.38(3), b = 376.87(2), c = 689.53(4) pm, V = 0.16225(2) nm3, R1 = 0.0141, and wR2 = 0.0323 for HP‐SmOF, and a = 620.02(4), b = 374.24(3), c = 686.82(5) pm, V = 0.15937(2) nm3, R1 = 0.0177, and wR2 = 0.0288 for HP‐EuOF. Calculations of the bond valence sums clearly showed that the oxygen atoms occupy the tetrahedrally coordinated position, whereas the fluorine atoms are fivefold coordinated in form of distorted square‐pyramids. The crystal structures and properties of HP‐REOF (RE = Nd, Sm, Eu) are discussed and compared to the isostructural phases and the normal‐pressure modifications of REOF (RE = Nd, Sm, Eu). Furthermore, results of investigations by EDX and Raman measurements including quantum mechanical calculations are presented.  相似文献   

2.
The quaternary germanides RE3TRh4Ge4 (RE = Ce, Pr, Nd; T = Nb, Ta) were synthesized from the elements by arc‐melting and subsequent annealing in a muffle furnace. The structure of Ce3TaRh4Ge4 was refined from single‐crystal X‐ray diffractometer data: new type, Pbam, a = 719.9(2), b = 1495.0(3), c = 431.61(8), wR2 = 0.0678, 1004 F2 values, and 40 variables. Isotypy of the remaining phases was evident from X‐ray powder patterns. Ce3TaRh4Ge4 is a new superstructure variant of the aristotype AlB2 with an ordering of cerium and tantalum on the aluminum site, whereas the honey‐comb network is built up by a 1:1 ordering of rhodium and germanium. This crystal‐chemical relationship is discussed based on a group‐subgroup scheme. The distinctly different size of tantalum and cerium leads to a pronounced puckering of the [Rh4Ge4] network, which shows the shortest interatomic distances (253–271 pm Rh–Ge) within the Ce3TaRh4Ge4 structure. Another remarkable structural feature concerns the tantalum coordination with six shorter Ta–Rh bonds (265–266 pm) and six longer Ta–Ge bonds (294–295 pm). The [Rh4Ge4] network fully separates the tantalum and cerium atoms (Ce–Ce > 387 pm, Ta–Ta > 431 pm, and Ce–Ta > 359 pm). The electronic density of states DOS from DFT calculations show metallic behavior with large contributions of localized Ce 4f as well as itinerant ones from all constituents at the Fermi level but no significant magnetic polarization on Ce could be identified. The bonding characteristics described based on overlap populations illustrate further the crystal chemistry observations of the different coordination of Ce1 and Ce2 in Ce3TaRh4Ge4. The Rh–Ge interactions within the network are highlighted as dominant. The bonding magnitudes follow the interatomic distances and identify differences of Ta bonding vs. Ce1/Ce2 bonding with the Rh and Ge substructures.  相似文献   

3.
New ternary rare earth metal boride carbides with compositions close to RE10B9C10 (RE = Gd, Tb) were prepared from the elements by melting around 1800 K followed by annealing in silica tubes at 1270 K for one month. The crystal structure of the terbium compound was solved by single‐crystal X‐ray diffraction. It crystallizes in a new structure type in the monoclinic space group P21/c, a = 7.937(1), b = 23.786(2), c = 11.172(1) Å, β = 133.74(1)°, Z = 4, R1 = 0.045 (wR2 = 0.11) for 5713 reflections with Io > 2σ(Io). In the structure BC2 units and single carbon atoms are attached to a zigzag boron chain forming the unprecedented B18C18 branching unit with a B–B distance of 2.42(2) Å between these units. In addition isolated carbon atoms occupy the centres of elongated octahedra formed by rare earth metal atoms. Disorder in the terbium position together with anomalous displacement ellipsoids for carbon atoms except of those in the BC2 fragments can be rationalized in terms of a slight deviation in stoichiometry, Tb10B9+xC10–x (x ≈? 0.2). The terbium compound is ferromagnetic below TC ≈? 45 K. Due to the presence of moderately narrow domain walls the magneto‐crystalline energy is small.  相似文献   

4.
The rare earth‐rich compounds RE23Rh7Mg4 (RE = La, Ce, Pr, Nd, Sm, Gd) were prepared by induction‐melting the elements in sealed tantalum tubes. The new compounds were characterized by X‐ray powder diffraction. They crystallize with the hexagonal Pr23Ir7Mg4 type structure, space group P63mc. The structures of La23Rh7Mg4 (a = 1019.1(1), c = 2303.7(4) pm, wR2 = 0.0827, 1979 F2 values, 69 variables), Nd23Rh7Mg4 (a = 995.4(2), c = 2242.3(5) pm, wR2 = 0.0592, 2555 F2 values, 74 variables) and Gd23Rh6.86(5)Mg4 (a = 980.5(2), c = 2205.9(5) pm, wR2 = 0.0390, 2083 F2 values, 71 variables) were refined from single crystal X‐ray diffractometer data. The three crystallographically different rhodium atoms have trigonal prismatic rare earth coordination with short RE–Rh distances (283–300 pm in Nd23Rh7Mg4). The prisms are condensed via common edges, leading to a rigid three‐dimensional network in which isolated Mg4 tetrahedra (312–317 pm Mg–Mg in Nd23Rh7Mg4) are embedded. Temperature dependent magnetic susceptibility data of Ce23Rh7Mg4 indicate Curie‐Weiss behavior with an experimental magnetic moment of 2.52(1) μB/Ce atom, indicative for stable trivalent cerium. Antiferromagnetic ordering is evident at 2.9 K.  相似文献   

5.
用高温固相法合成了系列化合物RE0.06La0.94M2O6Br(M=Nb,Ta;RE=Eu,Tb,Pr,Sm),并测定了其激发和发射光谱,室温下Eu3+、Tb3+、Pr3+、Sm3+在稀土-铌(钽)复合溴氧化物中呈现特征激发谱线,但Nb和Ta的光谱特性稍有不同。  相似文献   

6.
The new rare earth metal rich intermetallic compounds RE4CoMg (RE = Y, La, Pr, Nd, Sm, Gd–Tm) were prepared via melting of the elements in sealed tantalum tubes in a water‐cooled sample chamber of a high‐frequency furnace. The compounds were investigated by X‐ray diffraction of powders and single crystals: Gd4RhIn type, , a = 1428.38(9) pm, wR2 = 0.0638, 680 F2 values, 20 variables for La4CoMg, a = 1399.5(2) pm, wR2 = 0.0584, 589 F2 values, 20 variables for Pr4CoMg, a = 1390.2(3) pm, wR2 = 0.0513, 634 F2 values, 20 variables for Nd3.90CoMg1.10, a = 1381.0(3) pm, wR2 = 0.0730, 618 F2 values, 22 variables for Sm3.92Co0.93Mg1.08, a = 1373.1(4) pm, wR2 = 0.0586, 611 F2 values, 20 variables for Gd3.92CoMg1.08, a = 1362.1(3) pm, wR2 = 0.0576, 590 F2 values, 20 variables for Tb3.77CoMg1.23, a = 1344.8(2) pm, wR2 = 0.0683, 511 F2 values, 20 variables for Dy3.27CoMg1.73, and a = 1343.3(2) pm, wR2 = 0.0560, 542 F2 values, 20 variables for Er3.72CoMg1.28. The cobalt atoms have trigonal prismatic rare earth coordination. Condensation of the CoRE6 prisms leads to a three‐dimensional network which leaves larger voids that are filled by regular Mg4 tetrahedra at a Mg–Mg distance of 316 pm in La4CoMg. The magnesium atoms have twelve nearest neighbors (3 Mg + 9 RE) in icosahedral coordination. In the structures with Nd, Sm, Gd, Tb, Dy, and Er, the RE1 positions which are not involved in the trigonal prismatic network reveal some RE1/Mg mixing and the Sm3.92Co0.93Mg1.08 structure shows small cobalt defects. Considering La4CoMg as representative of all studied systems an analysis of the chemical bonding within density functional theory closely reproduces the crystal chemistry scheme and shows the role played by the valence states of the different constituents in the electronic band structure. Strong bonding interactions were observed between the lanthanum and cobalt atoms within the trigonal prismatic network.  相似文献   

7.
Two new intermetallic alkaline‐earth palladium borides, SrPd4B and BaPd4B were synthesised and their physical properties were investigated. The crystal structure of SrPd4B was solved from powder X‐ray diffraction data: new structure type, space group Pnma, a = 6.0014(1) Å, b = 5.5041(1) Å, c = 11.8723(2) Å, RI = 0.065, RP = 0.093. BaPd4B is isostructural with a = 6.0883(1) Å, b = 5.6066(1) Å, c = 12.0050(2) Å, RI = 0.062, RP = 0.097. The relationship of this structure type with the series of derivatives of the CaCu5 type is discussed. Calculated electronic band structures for palladium, Pd3B, SrPd5, SrPd4B and SrPd3B are compared. The role of boron and strontium for the electronic properties is discussed in detail. SrPd4B shows metallic behaviour with a DOS(EF) ≈? 1.7 eV–1 · f.u.–1 at the Fermi level. Magnetic properties, electrical resistivity and specific heat capacity measurements reveal that the two compounds are diamagnetic metallic conductors with low electronic density of states, in agreement, with the electronic structure calculations.  相似文献   

8.
The ternary indium compounds RE4Pd10In21 (RE = La, Ce, Pr, Nd, Sm) were synthesized from the elements in glassy carbon crucibles in a high‐frequency furnace. Single crystals of Sm4Pd10In21 were obtained from an indium flux. An arc‐melted precursor alloy of the starting composition ~SmPd3In6 was annealed with a slight excess of indium at 1200 K followed by slow cooling (5 K/h) to 870 K. All compounds were investigated by X‐ray powder diffraction and the structures were refined from single crystal diffractometer data. The RE4Pd10In21 indides are isotypic with Ho4Ni10Ga21, space group C2/m: a = 2314.3(2), b = 454.70(7), c = 1940.7(2) pm, β = 133.43(2)°, wR2 = 0.0681, 1678 F2 values for La4Pd10In21, a = 2308.2(1), b = 452.52(4), c = 1944.80(9) pm, β = 133.40(1)°, wR2 = 0.0659, 1684 F2 values for Ce4Pd10In21, a = 2303.8(2), b = 450.78(4), c = 1940.6(1) pm, β = 133.39(1)°, wR2 = 0.0513, 1648 F2 values for Pr4Pd10In21, a = 2300.2(2), b = 449.75(6), c = 1937.8(2) pm, β = 133.32(1)°, wR2 = 0.1086, 1506 F2 values for Nd4Pd10In21, and a = 2295.6(2), b = 447.07(4), c = 1935.7(1) pm, β = 133.16(1)°, wR2 = 0.2291, 2350 F2 values for Sm4Pd10In21, with 108 variables per refinement. All palladium atoms have a trigonal prismatic coordination. The strongest bonding interactions occur for the Pd—In and In—In contacts. The structures are composed of covalently bonded three‐dimensional [Pd10In21] networks in which the rare earth metal atoms fill distorted pentagonal channels. The crystal chemistry and chemical bonding in these indides is briefly discussed. Magnetic susceptibility measurements show diamagnetism for La4Pd10In21 and Curie‐Weiss paramagnetism for Ce4Pd10In21, Pr4Pd10In21, and Nd4Pd10In21. The neodymium compound orders antiferromagnetically at TN = 4.5(2) K and undergoes a metamagnetic transition at a critical field of 1.5(2) T. All the RE4Pd10In21 indides studied are metallic conductors.  相似文献   

9.
New ternary metal borides with compositionR. E. T 4B4 (R. E.=rare earth metal,T=transition metal) have been synthesized within the systems [La,Ce,Pr,Nd,Sm]–Os–B and [Y, La, Ce, Pr, Nd, Sm, Gd, Tb]–Ir–B. All compounds were found to be crystallizing with NdCo4B4-type structure. Magnetic measurements (80–300 K,Curie-Weiss behaviour, p ~ 16K and µeff=9.94µB for TbIr4B4) indicate Y andR. E. elements (except Ce) to be trivalent in these compounds. The crystal chemistry of the isotypic series [Y,R. E.] [Os,Ir]4B4 is discussed.
Ternäre Metallboride. [La,Ce,Pr,Nd,Sm] Os4B4 und [Y,La,Ce,Pr,Nd,Sm,Gd,Tb] Ir4B4 mit NdCo4B4-Struktur
Zusammenfassung Es wurden neue Metallboride der ZusammensetzungR. E. T 4B4 (R. E.=Seltenerdmetall,T=Übergangsmetall) innerhalb der Systeme [La,Ce, Pr,Nd,Sm]–Os–B und [Y,La,Ce,Pr,Nd,Sm,Gd,Tb]–Ir–B hergestellt. Alle Verbindungen kristallisieren entsprechend dem NdCo4B4-Typ. Magnetische Messungen (80–300K,Curie-Weiss-Verhalten, p ~ 16K und µeff=9.94µB für TbIr4B4) zeigen an daß Y und dieR. E.-Elemente (ausgenommen Ce) in diesen Verbindungen trivalent sind. Die Kristallchemie der isotypen [Y,R. E.][Os,Ir]4B4-Verbindungen wird diskutiert.
  相似文献   

10.
The magnetic data of RE2MnGe6 (RE = La, Ce) and YMn0.3Ge2 are reported. La2MnGe6 and Ce2MnGe6 crystallize in the orthorhombic Ce2CuGe6 structure type, space group Amm2 (No. 38). The non-stoichiometric YMn0.3Ge2 compound crystallizes with the orthorhombic CeNiSi2-type structure (space group Cmcm (No. 36)). The studied RE2MnGe6 (RE = La, Ce) intermetallics are characterized by ferromagnetic properties with Curie temperatures 177 (La) and 150 K (Ce), respectively. For YMn0.3Ge2 the low-field magnetic measurements indicate the antiferromagnetic property below 395 K with the small ferromagnetic component. The values of the magnetic moments in the ordered state indicate the ferromagnetic ordering in La2MnGe6 and complex magnetic order with the ferromagnetic component in YMn0.3Ge2 and Ce2MnGe6. The hysteresis loop and values of the coercivity field indicate that these compounds are soft magnetic materials.  相似文献   

11.
12.
Two new series of tetracyanamidogermanates were prepared by solid‐state reaction of appropriate amounts of REF3 (RE = rare earth), A2[GeF6] (A = alkaline), and Li2(CN2) in evacuated silica tubes. Powder X‐ray diffraction patterns of crystalline samples of KRE[Ge(CN2)4] and CsRE[Ge(CN2)4] were indexed isotypically to KRE[Si(CN2)4] and RbRE[Ge(CN2)4], respectively. Luminescence properties of Ce3+, Eu3+, and Tb3+ doped compounds and non‐linear optical properties (NLO) of KRE[Ge(CN2)4] are reported.  相似文献   

13.
钕, 铈掺杂的正极材料尖晶石型LiMn2O4的制备及性能   总被引:6,自引:0,他引:6  
通过掺杂不同含量的Nd,Ce制备LiMn2-xRExO4(RE=Ce,Nd;x=0,0.05,0.1,0.15,0.2)锂离子电池正极材料,研究稀土元素拓杂对尖晶石LiMn2O4正极材料电化学性质的影响。掺杂Nd,Ce后LiMn2O4正极材料更适合于锂离子的嵌入和脱出,电池的循环性能提高,但充放电容量随掺杂量的增加而下降。X射线光电子能谱分析表明掺杂Nd,Ce的LiMn2O4正极材料,其Mn^4+  相似文献   

14.
The crystal structures of 3[RE2(ADC)3(H2O)6] · 2H2O (RE = Pr, Nd, Sm, Eu, Tb, Dy) were solved and refined from X‐ray single crystal data. They crystallize in a structure type already known for RE = La, Ce and Gd (P1 , no. 2, Z = 2), which is characterized by REO9 polyhedra forming dimeric units being the nodes of a 3D framework structure linked by ADC2– anions (O2C–C≡C–CO2 = acetylenedicarboxylate). From synchrotron powder diffraction data it was shown that isostructural coordination networks are formed for RE = Ho, Er, Y, whereas for RE = Tm, Yb, Lu a new structure type crystallizing in a highly complex crystal structure with a large orthorhombic unit cell is found. All compounds are obtained by slow evaporation of an aqueous solution containing RE(OAc)3 · xH2O and acetylenedicarboxylic acid (H2ADC). The coordination networks of composition 3[RE2(ADC)3(H2O)6] · 2H2O were thoroughly investigated by thermal analysis and for RE = Eu, Tb, a strong red and green photoluminescence was observed and investigated by means of UV/Vis spectroscopy.  相似文献   

15.
The series of compounds REAu2In4 (RE = La, Ce, Pr, Nd) crystallize from excess In as rod-shaped single crystals. All members adopt the orthorhombic space group Pnma with a = 18.506(2) A, b = 4.6865(6) A, and c = 7.3414(9) A for LaAu2In4, a = 18.514(3) A, b = 4.6624(8) A, and c = 7.389(1) A for CeAu2In4, a = 18.420(4) A, b = 4.6202(9) A, and c = 7.376(2) A for the Pr analogue, and a = 18.406(2) A, b = 4.6114(5) A, and c = 7.4073(7) A for NdAu2In4. The REAu2In4 series can be regarded as polar intermetallic phases composed of a complex [Au2In4]3- polyanion network in which the rare-earth ions are embedded. The [Au2In4]3- network features In tetramer units, which defines the compounds as polyindides. Magnetic measurements found no magnetic ordering down to 2 K for any of the compounds. In addition, LaAu2In4 was found to be Pauli paramagnetic with a small susceptibility. Ab initio density functional methods were used to carry out electronic structure calculations to explore the bonding, the role of gold, and the contributions of different atoms to the density of states near the Fermi energy. We find that the density of states decreases slowly near Ef and reaches a minimum at about 0.5 eV above Ef.  相似文献   

16.
A series of isotypic rare‐earth metal pentagermanides including the new compound TbGe5 were prepared by high‐pressure synthesis. They crystallize in the orthorhombic space group Immm [No. 71; a = 395.70(9) pm; b = 611.1(2) pm, and c = 983.6(3) pm for TbGe5]. The crystal structure is isotypic to LaGe5 and consists of puckered germanium slabs, which sandwich a second germanium species and the rare‐earth metal atoms. At ambient pressure, the thermal decomposition of the phases REGe5 (RE = La, Nd, Sm, Gd, and Tb) proceeds via discrete intermediate steps into Ge(cF8) and thermodynamically stable germanium‐poorer phases. The investigated compounds REGe5 are paramagnetic metallic conductors, which order antiferromagnetically at low temperatures. Specific heat measurements reveal that the superconducting state of LaGe5 below Tc = 7.1(1) K is characterized by a critical field of μ0Hc2 = 0.2 T and weak electron‐phonon coupling. Density‐functional based band‐structure calculations yield a very similar electronic structure for all the isotypic REGe5 compounds. Besides a slight increase in the width of the valence band for smaller RE atoms, only minor differences are found for the two different germanium environments.  相似文献   

17.
The rare‐earth phosphide carbides RE4[P1–x(C2)x]3 (RE = La, Ce, Pr, Nd) represent the first example of a mixed anionic substructure formed by phosphorus and carbon, being the first step toward the formation of the mixed inorganic P–C species. The peculiarities of the crystal structure, magnetic properties, XAS data, and quantum chemical calculation results confirm the ionic nature of the interaction between the rare‐earth cations RE and phosphorus anions, while complex interaction of π states of the C2 anions and d (and/or f) states of the RE components is indicated. Thus, despite the extensive chemical analogy between the phosphide carbides and phosphide silicides, the atomic interactions stabilizing the structural motif are slightly different.  相似文献   

18.
The quaternary rare-earth phosphides RECuZnP2 (RE=Pr, Nd, Gd-Tm, Lu) have been prepared by reaction of the elements at 900 °C, completing this versatile series which forms for nearly all RE metals. They adopt the trigonal CaAl2Si2-type structure (Pearson symbol hP5, space group P3?m1, Z=1), as confirmed by single-crystal X-ray diffraction analysis on ErCuZnP2 and powder X-ray diffraction analysis on the remaining members. The Cu and Zn atoms are assumed to be disordered over the single transition-metal site. Band structure calculations on a hypothetically ordered YCuZnP2 model suggest a semimetal, with a zero band gap between the valence and conduction bands. This electronic structure is supported by XPS valence band spectra for RECuZnP2 (RE=Gd-Er), in which the intensity drops off smoothly at the Fermi edge. The absence of a band gap permits the electron count to deviate from the precise value of 16 e per formula unit, as demonstrated by the formation of a solid solution in GdCuxZn2−xP2 (1.0≤x≤1.3), while still retaining the CaAl2Si2-type structure. Because the Cu 2p XPS spectra indicate that the Cu atoms are always monovalent, the substitution of Cu for Zn leads to a decrease in electron count and a lowering of the Fermi level in the valence band. The magnetic susceptibility of RECuZnP2 (RE=Gd-Er), which obeys the Curie-Weiss law, confirms the presence of trivalent RE atoms.  相似文献   

19.
20.
The title compounds are prepared by high‐frequency melting of the elements in Nb ampules followed by annealing at 900 K for 2 h.  相似文献   

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