ABSTRACT
We have reported the density functional theory investigations on the monolayered, 2 layered and bulk MoSi2N4 in three structural modifications called α1 [Y.-L. Hong, et al., Chemical Vapor Deposition of Layered Two-Dimensional MoSi2N4 Materials, Science, 2020, 369(6504), 670-674, DOI: 10.1126/science.abb7023], α2 and α3 [Y. Yin, Q. Gong, M. Yi and W. Guo, Emerging Versatile Two-Dimensional MoSi2N4 Family, Adv. Funct. Mater., 2023, 2214050, DOI: 10.1002/adfm.202214050]. We showed that in the case of monolayers the difference in total energies is less than 0.1 eV between α1 and α3 phases, and less than 0.2 eV between α1 and α2 geometries. The most energetically favorable layer stacking for the bulk structures of each phase was investigated. All considered modifications are dynamically stable from a single layer to a bulk structure in energetically favorable stacking. Raman spectra for the monolayered, 2 layered and bulk structures were simulated and the vibrational analysis was performed. The main difference in the obtained spectra is associated with the position of the strongest band which depends on the Mo-N bond length. According to the obtained data, we can conclude that the Raman line at 348 cm-1 in the experimental spectra of MoSi2N4 can have more complex explanation than just Γ-point Raman-active vibration as was discussed before in [Y.-L. Hong, et al., Chemical Vapor Deposition of Layered Two-Dimensional MoSi2N4 Materials, Science, 2020, 369(6504), 670-674, DOI: 10.1126/science.abb7023].
ABSTRACT
Single crystals of SmAl3(BO3)4 were synthesized by the group growth on seeds method. The crystal structure was solved using a single-crystal experiment and the purity of the bulk material was proved by the Rietveld method. This borate crystallizes in the monoclinic C2/c space group with unit-cell parameters a = 7.2386â (3), b = 9.3412â (5), c = 11.1013â (4)â Å and ß = 103.2240â (10)°. IR and Raman spectroscopic analyses confirmed the monoclinic structure of SmAl3(BO3)4. Under 532.1â nm excitation, luminescence spectra exhibit bands assignable to the transitions from 4G5/2 to 6H5/2, 6H7/2, 6H9/2 and 6H11/2. The similarity of the luminescence spectra of the trigonal and monoclinic polymorphs is explained by the minor role of Sm-O bond distortion and the primary role of rotational distortion of SmO6 octahedra. The smaller covalency of the Sm-O bond in alumoborates is deduced in comparison with galloborates. Calorimetric measurements did not reveal high-temperature structural phase transitions up to a temperature of 720â K.
ABSTRACT
The oxidation process of samariumoxysulfide was studied in the temperature range of 500-1000 °C. Our DTA investigation allowed for establishing the main thermodynamic (∆Hºexp = -654.6 kJ/mol) and kinetic characteristics of the process (Ea = 244 kJ/mol, A = 2 × 1010). The enthalpy value of samarium oxysulfate (ΔHºf (Sm2O2SO4(monocl)) = -2294.0 kJ/mol) formation was calculated. The calculated process enthalpy value coincides with the value determined in the experiment. It was established that samarium oxysulfate crystallizes in the monoclinic symmetry class and its crystal structure belongs to space group C2/c with unit cell parameters a = 13.7442 (2), b = 4.20178 (4) and c = 8.16711 (8)Å, ß = 107.224 (1)°, V = 450.498 (9)Å3, Z = 4. The main elements of the crystalline structure are obtained and the cation coordination environment is analyzed in detail. Vibrational spectroscopy methods confirmed the structural model adequacy. The Sm2O2SO4luminescence spectra exhibit three main bands easily assignable to the transitions from 4G5/2 state to 6H5/2, 6H7/2, and 6H9/2 multiplets.
Subject(s)
Samarium/chemistry , Luminescence , Oxidation-Reduction , Temperature , ThermodynamicsABSTRACT
Crystal structure of LaF3 single crystal is refined in tysonite-type trigonal unit cell P [Formula: see text] c1 using density functional theory calculations and Raman spectroscopy. It is shown that trigonal structure with P [Formula: see text] c1 space group is more energy-efficient than hexagonal structure with space group P63 cm. Simulated Raman spectra obtained using LDA approximation is in much better agreement with experimental data than that obtained with PBE and PBEsol functionals of GGA. The calculated frequency value of silent mode B 2 in case of hexagonal structure P63 cm was found to be imaginary (unstable mode), thus the energy surface obtains negative curvature with respect to the corresponding normal coordinates of the mode which leads to instability of the hexagonal structure in harmonic approximation. The A 1g line at 214 cm-1 in Raman spectra of LaF3 related to the translation of F2 ions along c axis can be connected with F2 ionic conductivity.
ABSTRACT
Two ammonium oxofluorovanadates, (NH4)3VO2F4 and (NH4)3VOF5, have been investigated by temperature-dependent infrared and Raman spectroscopy methods to determine the nature of phase transitions (PT) in these compounds. Dynamics of quasioctahedral groups was simulated within the framework of semi-empirical approach, which justified the cis-conformation of VO2F43- (C2v) and the C4v geometry of VOF53-. The observed infrared and Raman spectra of both compounds at room temperature (RT) revealed the presence at least of two crystallographically independent octahedral groups. The first order PT at elevated temperatures is connected with a complete dynamic disordering of these groups with only single octahedral state. At lower temperatures, the octahedra are ordered and several octahedral states appear. This PT is the most pronounced in the case of (NH4)3VOF5, when at least seven independent VOF53- octahedra are present in the structure below 50K, in accordance with the Raman spectra. Ammonium groups do not take part in PTs at higher and room temperatures but their reorientational motion freezes at lower temperatures.
