Rationale for the sluggish oxidative addition of aryl halides to Au(I)

The oxidative addition of Csp2–Br or Csp2–I bonds to gold(I) does not take place even under very favorable intramolecular conditions that could form five- or six-membered gold(III) metallacycles. DFT calculations reveal that although this process could be feasible thermodynamically, it is kinetically very sluggish

Chemical Processes Involved in Atomic Layer Deposition of Gallium Sulfide: Insights from Theory

Growth characteristics of atomic layer deposition (ALD) of gallium sulfide (Ga_<i>x</i>S) from tris­(dimethylamino)­gallium (Ga­(NMe₂)₃) and hydrogen sulfide (H₂S) have been investigated by density functional theory. The steady-state film growth during one ALD cycle was modeled by studying the energetics of a large set of reactions taking place on a surface described as a SH-terminated gallium sulfide (Ga₂S₃) cluster. The opportunity of using gas-phase cluster calculations to compute entropic contributions is discussed. Detailed reaction mechanisms are provided, along with free energy profiles and a large reaction network emerges. It confirms a ligand loss/exchange mechanism, and various aspects of the growth are explored (fate of the precursor and co-reactant, self-saturation of the surface, crawling and cooperative effects, role of the amido ligand, of the impurities, etc.) and confronted to experimental observations. All the key reaction steps are facile and thermodynamically favorable, while undesired side reactions are more demanding energetically

Collective Behavior of Molecular Dipoles in CH₃NH₃PbI₃

Using ab initio molecular dynamics, we report a detailed exploration of the thermal motion occurring in perovskite crystals of the formula CH₃NH₃PbI₃. We exploit the data generated to obtain estimates of the rotational relaxation time of the cation CH₃NH₃⁺. We examine the tetragonal and cubic phases, as both may be present under operational conditions. Influenced by each other, and by the tilting of PbI₆ octahedra, cations undergo collective motion as their contribution to polarization does not vanish. We thereby qualitatively describe the modus operandi of formation of microscopic ferroelectric domains

Collective Behavior of Molecular Dipoles in CH₃NH₃PbI₃

Using ab initio molecular dynamics, we report a detailed exploration of the thermal motion occurring in perovskite crystals of the formula CH₃NH₃PbI₃. We exploit the data generated to obtain estimates of the rotational relaxation time of the cation CH₃NH₃⁺. We examine the tetragonal and cubic phases, as both may be present under operational conditions. Influenced by each other, and by the tilting of PbI₆ octahedra, cations undergo collective motion as their contribution to polarization does not vanish. We thereby qualitatively describe the modus operandi of formation of microscopic ferroelectric domains