N. E. Novikova

Structure of KTiOAsO4 single crystals at 293 and 30 K

The unit cell parameters of KTiOPO4 and KTiOAsO4 single crystals are measured in the temperature range from room temperature to 20 K. It is found that the unit cell volume of the single crystals changes smoothly. With a decrease in temperature, the c parameter remains almost unchanged. In a certain temperature range, the linear temperature dependence of the a and b parameters is violated. An X-ray diffraction study of KTiOAsO4 single crystals is performed at T = 293 and 30 K. With a decrease in temperature, the electron density in the channels of the structure undergoes a redistribution, suggesting that at room temperature the state of the potassium ions is characterized by the dynamic and static disordering. The nonuniformity of the distribution of the electron density at the junctions of TiO6 octahedra and AsO4 tetrahedra is significantly enhanced in relation to that at the corresponding junctions in the KTiOPO4 structure. It has been experimentally established that the geometry of the tetrahedral anions makes a decisive contribution to the nonlinearity of KTiOAsO4 single crystals.

Crystal structure of the metastable cubic βms phase of La2Mo2O9 single crystal at T = 33 K

The structure of the cubic metastable βms phase of La2Mo2O9 single crystal has been precisely investigated by X-ray diffraction at 33 K for the first time. The measurement of the unit-cell parameter of this crystal in the range from room temperature to 33 K showed that the unit-cell parameter and volume change continuously in this range. The crystal has a similar structure at T = 33 K and at room temperature. A local lowering of the symmetry for La and Mo atoms, caused by their displacement, is confirmed, and a similar displacement (which was not observed at room temperature) is revealed for O(1) atoms. The thermal parameters for O(2) and O(3) atoms do not change with a decrease in temperature, in contrast to the thermal parameters of Mo, La, and O(1) atoms. This fact indicates that the O(2) and O3 atoms in this crystal are statically disordered.

Synthesis, properties, and structure of potassium titanyl phosphate single crystals doped with hafnium

Single crystals of potassium titanyl phosphate doped with hafnium are grown by spontaneous flux crystallization. Their physical properties are studied, and the structure of three KTi1 − xHfxOPO4 crystals (x = 0.01, 0.03, and 0.12) is determined. In the crystals studied, hafnium mostly occupies the second titanium position. The doping of KTP crystals with hafnium results in an elongation of K-O bonds in the potassium polyhedra and, as a consequence, in a considerable (by approximately 180°C) decrease in the temperature of ferroelectric phase transition. The magnitude of anomalous permittivity substantially decreases. The electrical conduction in the specimens studied decreases by approximately half an order of magnitude in the low-temperature region but remains almost unchanged in the high-temperature region. Even at minor concentrations, the presence of a hafnium additive in the specimens considerably (by 35%) enhances the intensity of the second harmonic generation of laser radiation.

Structural reasons for the nonlinear optical properties of KTi0.96Zr0.04OPO4 single crystals

This paper reports on the results of the precision X-ray structural investigations of KTi0.96Zr0.04OPO4 single crystals at room temperature. It is established that the incorporation of zirconium atoms into the structure of KTiOPO4 (KTP) crystals does not lead to substantial changes in the framework structure and results only in an insignificant decrease in the scatter of the distances in the PO4 tetrahedra and the formation of more symmetric (TiZr)O6 octahedra as compared to the TiO6 octahedra. However, the incorporation of zirconium atoms into the KTP structure is accompanied by the redistribution of the electron density in the crystal as a whole, so that the electron density increases in the region of the positions occupied by the potassium atoms. This changes the nonlinear optical properties of the given series of crystals, which are estimated from the intensity of the second harmonic generation signals.

Structure of KTiOPO4 single crystals grown by the top-seeded solution and spontaneous flux crystallization methods

This paper reports on the results of precision X-ray structural investigations of KTiOPO4 single crystals grown by one method (crystallization from a solution in the melt) in two variants (the spontaneous formation of crystallization centers or top-seeded solution growth during slow cooling of saturated solution melts). It is shown that spontaneous flux crystallization leads to the formation of a larger number of defects. Potassium atoms are found to be disordered. The splitting of the K1 and K2 potassium positions is equal to 0.347(4) and 0.279(3) Å, respectively, for the crystals grown by the top-seeded solution method and 0.308(5) and 0.321(4) Å, respectively, for the crystals grown through the spontaneous flux crystallization.

Structural study of K0.93Ti0.93Nb0.07OPO4 single crystals at 30 K

The structure of a K0.93Ti0.93Nb0.07OPO4 single crystal is studied at the temperature 30 K. The measurements are performed on a four-circle HUBER-5042 diffractometer with a DISPLEX DE-202 cryostat. Processing of the diffraction data and the preliminary refinement of the model are performed using the ASTRA program package. The final refinement of the structure model is made using the JANA2000 program complex. The refinement shows that the structure of a K0.93Ti0.93Nb0.07OPO4 crystal at T = 30 K is similar to its structure at room temperature. No phase transitions are revealed. Slight temperature-induced displacements of the potassium positions in the large cavities of the mixed framework are established.

Single-crystal structure of Nd{sub 5}Mo{sub 3}O{sub 16} at T = 30 K

A precision X-ray diffraction study of Nd5Mo3O16 single crystals is performed for the first time at 30 K. Measurements in the range from room temperature to 30K showed that the unit-cell parameters and volume change smoothly. The crystal structure at T = 30 K is similar to that at room temperature. The model of splitting of the atomic positions is confirmed.

Single-crystal structure of Nd5Mo3O16 at T = 30 K

A precision X-ray diffraction study of Nd5Mo3O16 single crystals is performed for the first time at 30 K. Measurements in the range from room temperature to 30K showed that the unit-cell parameters and volume change smoothly. The crystal structure at T = 30 K is similar to that at room temperature. The model of splitting of the atomic positions is confirmed.

Single-crystal structure of vanadium-doped La2Mo2O9

A high-precision X-ray diffraction study of single crystals of two compositions—La2Mo1.78V0.22O8.89 and La2Mo1.64V0.36O8.82—was performed. In the vanadium-doped compounds, as in the structure of the metastable βms phase of pure La2Mo2O9, the La and Mo atoms and one of the three oxygen atoms are displaced from the threefold axis, on which they are located in the high-temperature β phase. The structure contains two partially occupied oxygen sites. It was shown that molybdenum atoms are partially replaced by vanadium atoms, which are not involved in the disordering, are located on the threefold axis, and are shifted toward one of the oxygen atoms. This is consistent with the temperature-induced changes in the structure of La2Mo2O9 and the changes in the properties of these crystals caused by the introduction of vanadium atoms into the structure.

Crystal structure of the cubic βms-phase of a La1.82Bi0.18Mo2O9 single crystal at 33 K

Single crystals of the cubic βms-phase of La1.82Bi0.18Mo2O9 have been characterized for the first time by precision X-ray diffraction at 33 K. The structure of a crystal determined at T = 33 K is identical to the structure studied at room temperature. It is confirmed that the La, Mo1, and O1 atoms deviate from their positions on the threefold axis in the high-temperature β-phase; part of lanthanum atoms is substituted by bismuth atoms, which are located on the threefold axis; part of the molybdenum atoms return to the position on the threefold axis.