Binuclear spin-crossover [Fe(bt)(NCS)2]2(bpm) complex: A study using first principles calculations.

The spin-crossover [Fe(bt)(NCS)2]2(bpm) complex is studied using spin-polarized density functional theory within the generalized gradient approximation, the Hubbard U and the weak van der Waals interactions in conjunction with the projector augmented wave method in its molecular and periodic arrangements. It is shown that the considered complex has three magnetic configurations [high spin state (HS)-HS, HS-low spin state (LS), and LS-LS] corresponding to those observed experimentally after two transition temperatures Tc (1) of 163 K and Tc (2) of 197 K. For the HS-HS magnetic state, we found that the two Fe centers are antiferromagnetically coupled for both molecular and periodic structures in good agreement with the experimental observations. Our results show that the computed total energy difference between the magnetic state configurations of the considered Fe2 complex is significantly smaller compared to those reported in the literature for other mono- or binuclear compounds.

Tuning the electronic and optical properties of small organic acenedithiophene molecular crystals for photovoltaic applications: First principles calculations.

Periodic density functional theory was employed to investigate the impact of chemical modifications on the properties of π-conjugated acenedithiophene molecular crystals. Here, we highlight the importance of the ß-methylthionation effect, the position of the sulfur atoms of the thiacycle group and their size, and the number of central benzene rings in the chemical modification strategy. Our results show that the introduction of the methylthio groups at the ß-positions of the thiophene and the additional benzene ring at the center of the BDT crystal structure are a promising strategy to improve the performance of organic semiconductors, as observed experimentally. We found that ß-MT-ADT exhibits large charge carrier mobility, which is in good agreement with the experimental results and comparable to that of rubrene. In addition, the electronic and optical properties of these ambipolar materials suggest promising performances with ß-MT-ADT > ADT >ß-MT-NDT > NDT > BEDT-BDT >ß-MT-BDT > BDT. Moreover, functionalization with thiacycle-fused sulfur atoms of different sizes and numbers improve the properties of BDT but is still less efficient than the methylthionation effect. Overall, our findings suggest a promising molecular modification strategy for possibly high performance ambipolar organic semiconducting materials.

First-principles study of the structural and electronic properties of tetragonal ZrOX (X = S, Se, and Te) monolayers and their vdW heterostructures for applications in optoelectronics and photocatalysis.

Using first-principles calculations, we have studied the structural and electronic properties of ZrOX (X = S, Se, and Te) monolayers and their van der Waals heterostructures in the tetragonal structure. Our results show that these monolayers are dynamically stable and are semiconductors with electronic bandgaps ranging from 1.98 to 3.16 eV as obtained with the GW approximation. By computing their band edges, we show that ZrOS and ZrOSe are of interest for water splitting applications. In addition, the van der Waals heterostructures formed by these monolayers show a type I band alignment for ZrOTe/ZrOSe and a type II alignment for the other two heterostructures, making them potential candidates for certain optoelectronic applications involving electron/hole separation.

Ternary Chalcogenides BaMxTe2 (M = Cu, Ag): Syntheses, Modulated Crystal Structures, Optical Properties, and Electronic Calculations.

Standard solid-state methods produced black crystals of the compounds BaCu0.43(3)Te2 and BaAg0.77(1)Te2 at 1173 K; the crystal structures of each were established using single-crystal X-ray diffraction data. Both crystal structures are modulated. The compound BaCu0.43(3)Te2 crystallizes in the monoclinic superspace group P2(αß1/2)0, having cell dimensions of a = 4.6406(5) Å, b = 4.6596(5) Å, c = 10.362(1) Å, ß = 90.000(9)°, and Z = 2 and an incommensurate vector of q = 0.3499(6)b* + 0.5c*. The compound BaAg0.77(1)Te2 crystallizes in the orthorhombic P21212(α00)000 superspace group with cell dimensions of a = 4.6734(1) Å, b = 4.6468(1) Å, c = 11.1376(3) Å, and Z = 2 and an incommensurate vector of q = 0.364(2)a*. The asymmetric unit of the BaCu0.43(3)Te2 structure comprises eight crystallographically independent sites; that for BaAg0.77(1)Te2 comprises four. In these two structures, each of the M (M = Cu, Ag) atoms is connected to four Te atoms to make two-dimensional layers of [MxTe4/4]n- that are separated by layers of Ba atoms and square nets of Te. A Raman spectroscopic study at 298(2) K on a pelletized polycrystalline sample of BaAg0.8Te2 shows the presence of Ag-Te (83, 116, and 139 cm-1) and Ba-Te vibrations (667 and 732 cm-1). A UV-vis-NIR spectroscopic study on a powdered sample of BaAg0.8Te2 shows the semiconducting nature of the compound with a direct band gap of 1.0(2) eV, consistent with its black color. DFT calculations give a pseudo bandgap with a weak value of the DOS at the Fermi level.

Grafting of iron on amorphous silica surfaces from ab initio calculations.

Iron over silica catalytic systems have attracted considerable attention due to their activity and selectivity in different reactions, for instance, in the hydrodeoxygenation process. Here, the grafting mechanisms of iron under various forms (one atom, two atoms, or a cluster) on silica surfaces are studied using ab initio calculations. Various geometries with different locations of iron on the silica structure have been investigated, and it is found that a strong interaction between iron and the silanol groups takes place, mostly driven by the formation of Fe-O-Si bonds, and in few cases by nearby surface OH groups, creating Fe-OH-Si bonds. For the cluster, we show that the most favorable adsorption mode induces a strong effect on the silica surface accompanied with a large charge transfer, making it very stable and promising for a large panel of applications.

Joint refinement model for the spin resolved one-electron reduced density matrix of YTiO3 using magnetic structure factors and magnetic Compton profiles data.

In this paper, we propose a simple cluster model with limited basis sets to reproduce the unpaired electron distributions in a YTiO3 ferromagnetic crystal. The spin-resolved one-electron-reduced density matrix is reconstructed simultaneously from theoretical magnetic structure factors and directional magnetic Compton profiles using our joint refinement algorithm. This algorithm is guided by the rescaling of basis functions and the adjustment of the spin population matrix. The resulting spin electron density in both position and momentum spaces from the joint refinement model is in agreement with theoretical and experimental results. Benefits brought from magnetic Compton profiles to the entire spin density matrix are illustrated. We studied the magnetic properties of the YTiO3 crystal along the Ti-O1-Ti bonding. We found that the basis functions are mostly rescaled by means of magnetic Compton profiles, while the molecular occupation numbers are mainly modified by the magnetic structure factors.

Theoretical study of the catalytic hydrodeoxygenation of furan, methylfuran and benzofurane on MoS2.

Herein, we have studied the direct deoxygenation (DDO) (without prior hydrogenation) of furan, 2-methylfuran and benzofuran on the metal edge of MoS2 with a vacancy created under pressure of dihydrogen. For the three molecules, we found that the desorption of the water molecule for the regeneration of the vacancy is the most endothermic. Based on the thermodynamic and kinetic aspects, the reactivity order of the oxygenated compounds is furan ≈ 2-methylfuran > benzofuran, which is in agreement with literature. We present the key stages of the mechanisms and highlight the effects of substituents.

Spin resolved electron density study of YTiO3 in its ferromagnetic phase: signature of orbital ordering.

The present work reports on the charge and spin density modelling of YTiO3 in its ferromagnetic state (T C = 27 K). Accurate polarized neutron diffraction and high-resolution X-ray diffraction (XRD) experiments were carried out on a single crystal at the ORPHÉE reactor (LLB) and SPRING8 synchrotron source. The experimental data are modelled by the spin resolved pseudo-atomic multipolar model (Deutsch et al., 2012 ▸). The refinement strategy is discussed and the result of this electron density modelling is compared with that from XRD measured at 100 K and with density functional theory calculations. The results show that the spin and charge densities around the Ti atom have lobes directed away from the O atoms, confirming the filling of the t 2g orbitals of the Ti atom. The d xy orbital is less populated than d xz and d yz , which is a sign of a partial lift of degeneracy of the t 2g orbitals. This study confirms the orbital ordering at low temperature (20 K), which is already present in the paramagnetic state above the ferromagnetic transition (100 K).

Development of a joint refinement model for the spin-resolved one-electron reduced density matrix using different data sets.

The paper describes a joint refinement model of the spin-resolved one-electron reduced density matrix using simultaneously magnetic structure factors and magnetic directional Compton profiles. The model is guided by two strategies: (i) variation of basis functions and (ii) variation of the spin population matrix. The implementation for a finite system is based on an expansion of the natural orbitals on basis sets. To show the potential benefits brought by the joint refinement model, the paper also presents the refinement results using magnetic structure factors only. The joint refinement model provides very satisfactory results reproducing the pseudo-data. In particular, magnetic Compton profiles have a strong effect not only on the off-diagonal elements of the spin-resolved one-electron reduced density matrix but also on its diagonal elements.

Exchange Coupling of Spin-Crossover Molecules to Ferromagnetic Co Islands.

The properties of Fe(1,10-phenanthroline)2(NCS)2 (Fe-phen) molecules deposited on Co/Cu(111) are studied with scanning tunneling microscopy (STM) operated in ultrahigh vacuum at low temperature (4 K) and ab initio calculations. Both the experimental and theoretical results are used to identify the high-spin (HS) state of Fe-phen. Additionally, the calculations reveal a strong spin-polarization of the density of states (DOS) and is validated experimentally using the spin sensitivity of spin-polarized STM. Finally, it is shown that the magnetic moment of the Fe-ion within HS Fe-phen is strongly magnetically coupled to the underlying magnetic Co through the NCS groups. These findings enable promising spintronic perspectives.