Polymorphism of CsGaS2 - structural characterization of a new two-dimensional polymorph and study of the phase-transition kinetics

CsGaS2-mC64 was obtained by reaction of CsN3 with stoichiometric amounts of Ga2S3 and S at elevated temperatures. The crystal structure of the air- and moisture stable compound was determined from single-crystal X-ray diffraction data. The colourless solid crystallizes in the monoclinic space group C2/c (no. 15) with the lattice parameters a = 10.5718(6) angstrom, b = 10.5708(6) angstrom, c = 16.0847(8) angstrom, ss = 99.445(4)degrees, V = 1773.1(2) angstrom(3), and Z = 16. The compound crystallizes in the TlGaSe2 structure type and features anionic layers (2)(infinity)[Ga4S84-] consisting of corner-sharing Ga4S10 supertetrahedra. At temperatures above 600 degrees C an irreversible phase-transition to CsGaS2-mC16 occurs. The phase-transition kinetics were studied using in situ high-temperature X-ray powder diffraction techniques. This transition can only be reversed by using high pressures (> 5 GPa at 500 degrees C). The compound was further characterized using Raman- and diffuse reflectance spectroscopy. Chemical bonding was analysed by DFT calculations

First principles calculations on structure, bonding, and vibrational frequencies of SiPsub 2

Pyrite type SiP2 is reinvestigated by first principles calculations on various levels of functionals including local density approximation, generalized gradient approximation, Becke-Lee-Yang-Parr hybrid functional, and the Hartree-Fock method. SiP2 is seen as a model compound with molecular [P–P] entities and [SiP6] octahedra. Structure and bonding are addressed by electronic structure calculations. Special attention is spent on P–P and Si–P bonds in terms of bond lengths and respective stretching modes from simulated Raman spectra. The electronic structure is analyzed in both direct and momentum space by the electron localization function and site projected density of states. The main goals of this work are to understand the nature of chemical bonding in SiP2 and to compare and contrast the different methods of calculation