ABSTRACT
The incommensurately modulated antiferroelectric phase of sodium nitrite, NaNO2, transforms at T(N) = 437.7 K to the short-range modulated paraelectric phase. The apparently discontinuous phase transition is accompanied by characteristic changes in the diffraction pattern. Contrary to the well known modulated structures with sharp satellite reflections, the diffraction pattern of a short-range modulated structure contains diffuse satellite reflections. The short-range modulated crystal structure of the paraelectric phase of sodium nitrite has been analysed by the Reverse Monte Carlo (RMC) simulation of X-ray diffuse scattering. The crystal structure of sodium nitrite may be regarded as consisting of [Na+NO2-]infinity rows running along the polar b axis. One can expect long fragments of rows with uniform polarity The assumption that single [Na+NO2-]infinity rows are polar with uniform polarity proved to be a convenient approximation which is in good agreement with the observed diffraction pattern. The distribution of (+)- and (-)-[Na+NO2-]infinity polar rows crossing the (010) plane of short-range modulated NaNO2 revealed by RMC shows nanodomains consisting of distorted fragments of a sinusoidally modulated crystal structure. The size of the nanodomains and the degree of order in paraelectric NaNO2 decreases with temperature.
Subject(s)
Crystallography, X-Ray/methods , Sodium Nitrite/chemistry , Kinetics , Models, Molecular , Monte Carlo Method , Phase Transition , Scattering, Radiation , Temperature , X-RaysABSTRACT
Crystals of uranium iodine phthalocyanine present an example of a disordered commensurate modulated structure of the intergrowth type. The short-range order of both uranium ions and iodine chains [I(3)(-)](n) has been analysed by Reverse Monte Carlo (RMC) simulation of X-ray diffuse scattering. The diffraction pattern of uranium iodine phthalocyanine contains diffuse superstructure reflections. In the routine crystal structure analysis diffuse superstructure reflections may be either omitted or measured and classified along with other Bragg reflections. The crystal structure of uranium iodine phthalocyanine is an example of such ambiguity. The crystal structures of two specimens of [U(1-x)Pc(2)]I(2-y) with slightly different composition have been published in the literature with different space groups and unit cells. We have shown that the structure of both specimens differs only in the degree of short-range order and is isostructural with [YbPc(2)]I(2). We have also shown that while the omission of diffuse reflections results in the average crystal structure, the treatment of these reflections as normal Bragg reflections is incorrect and produces the structure averaged over a limited small range.
ABSTRACT
Iodine-doped ytterbium phthalocyanine, C(64)H(32)N(16)YbI(2), [YbPc(2)]I(2) (YPI), presents an example of a disordered modulated crystal structure of the intergrowth type. The short-range order in YPI has been studied at ambient temperature by the diffuse X-ray scattering technique. Both Yb and I atoms are disordered. In a unit cell of the average structure, the Yb atoms occupy two positions, 1/2, 1/2, 1/4 or 1/2, 1/2, 3/4, with occupancy 0.5. In the neighbouring unit cells in the (001) plane there is, however, a strong tendency towards an alternating distribution of ytterbium in positions shifted by Delta z = 1/2. The crystal structure of YPI consists of one-dimensional columnar stacks of [YbPc(2)(2/3+)](n) and of linear iodine chains [I(3)(-)](n). The modulation is commensurate since the period c(I) of iodine chains [I(3)(-)](n) in the [001] direction is equal to one-half of the period c of the [YbPc(2)(2/3+)](n) stacks. In the crystal structure, each stack of [YbPc(2)(2/3+)](n) may occur in two settings shifted by c/2 and each iodine chain in three settings shifted along [001] by one-third of the period c(I). The short-range order of iodine chains distributed over three settings results in a complicated pattern. Iodine chains of the same setting tend to form ribbons perpendicular to <100> and running along [001].
