连续波锁模P_r~（3＋）：YLF激光器

本文报导了采用氩离子激光器来泵浦Ｒｒ￣（３＋）：ＹＬＦ晶体，应用声光调制器实现了主动锁模；同时应用振动─高反射平面镜也实现了被动锁模，两种锁模均得到了ｐｓ光脉冲。据作者了解这是这种晶体材料的第一次锁模运转。     

Double (n=2) and triple (n=3) [M4Bi2n−2O2n] polycationic ribbons in the new Bi∼3Cd∼3.72M∼1.28O5(PO4)3 oxyphosphate (M=Co, Cu, Zn)

The crystal structure of the new Bi_∼3Cd_∼3.72Co_∼1.28O₅(PO₄)₃ has been refined from single crystal XRD data, R₁=5.37%, space group Abmm, a=11.5322(28) Å, b=5.4760(13) Å, c=23.2446(56) Å, Z=4. Compared to Bi_∼1.2M_∼1.2O_1.5(PO₄) and Bi_∼6.2Cu_∼6.2O₈(PO₄)₅, this compound is an additional example of disordered Bi³⁺/M²⁺ oxyphosphate and is well described from the arrangement of double [Bi₄Cd₄O₆]⁸⁺ (=D) and triple [Bi₂Cd_3.44Co_0.56O₄]⁶⁺ (=T) polycationic ribbons formed of edge-sharing O(Bi,M)₄ tetrahedra surrounded by PO₄ groups. According to the nomenclature defined in this work, the sequence is TT/DtDt, where t stands for the tunnels created by PO₄ between two subsequent double ribbons and occupied by Co²⁺. The HREM study allows a clear visualization of the announced sequence by comparison with the refined crystal structure. The Bi³⁺/M²⁺ statistic disorder at the edges of T and D entities is responsible for the PO₄ multi-configuration disorder around a central P atom. Infrared spectroscopy and neutron diffraction of similar compounds (without the highly absorbing Cadmium) even suggests the long range ordering loss for phosphates. Therefore, electron diffraction shows the existence of a modulation vector q^*=1/2a^*+(1/3+ε)b^* which pictures cationic ordering in the (001) plane, at the crystallite scale. This ordering is largely lost at the single crystal scale. The existence of mixed Bi³⁺/M²⁺ positions also enables a partial filling of the tunnels by Co²⁺ and yields a composition range checked by solid state reaction. The title compound can be prepared as a single phase and also the M=Zn²⁺ term can be obtained in a biphasic mixture. For M=Cu²⁺, a monoclinic distortion has been evidenced from XRD and HREM patterns but surprisingly, the orthorhombic ideal form can also be obtained in similar conditions.     

Structural and P NMR investigation of Bi(MM′)2PO6 statistic solid solutions: Deconvolution of lattice constraints and cationic influences

Two solid solutions BiM_xMg_(2−x)PO₆ (with M²⁺=Zn or Cd) have been studied through ³¹P MAS NMR. The analysis has been performed on the basis of refined crystal structures through X-ray diffraction and neutron diffraction. The BiZn_xMg_(2−x)PO₆ does not provide direct evidence for sensitive changes in the phosphorus local symmetry. This result is in good agreement with structural data which show nearly unchanged lattices and atomic separations through the Zn²⁺ for Mg²⁺ substitution. On the other hand, the Cd²⁺ for Mg²⁺ substitution behaves differently. Indeed, up to five resonances are observed, each corresponding to one of the five first-cationic neighbour distributions, i.e. 4Mg/0Cd, 3Mg/1Cd, 2Mg/2Cd, 1Mg/3Cd and 0Mg/4Cd. Their intensities match rather well the expected weight for each configuration of the statistical Cd²⁺/Mg²⁺ mixed occupancy. The match is further improved when one takes into account the influence of the 2nd cationic sphere that is available from high-field NMR data (18.8 T). Finally, the fine examination of the chemical shift for each resonance versus x allows to de-convolute the mean Z/a² effective field into two sub-effects: a lattice constraint-only term and a chemical-only term whose effects are directly quantifiable.