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Phys Chem Chem Phys ; 25(12): 8664-8675, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36891959


This computational work is devoted to the investigation (MP2/def2-TZVP) of the geometry and IR parameters of arsinic acid H2AsOOH and its hydrogen-bonded complexes under vacuum and in media with different polarity. The medium effects were accounted for in two ways: (1) implicitly, using the IEFPCM model, varying the dielectric permittivity (ε) and (2) explicitly, by considering hydrogen-bonded complexes of H2As(O)OH with various hydrogen bond donors (41 complexes) or acceptors (38 complexes), imitating a gradual transition to the As(OH)2+ or AsO2- moiety, respectively. It was shown that the transition from vacuum to a medium with ε > 1 causes the As(O)OH fragment to lose its flatness. The solvent polar medium introduces significant changes in the geometry and IR spectral parameters of hydrogen-bonded complexes too: as the polarity of a medium increases, weak hydrogen bonds become weaker, and strong and medium hydrogen bonds become stronger; in the case of a complex with two hydrogen bonds cooperativity effects are observed. In almost all cases the driving force of these changes appears to be preferential solvation of charge-separated structures. In the limiting case of complete deprotonation (or conversely complete protonation) the vibrational frequencies of νAsO and νAs-O turn into νAs-O(asym) and νAs-O(sym), respectively. In the intermediate cases the distance between νAsO and νAs-O is sensitive to both implicit solvation and explicit solvation and the systematic changes of this distance can be used for estimation of the degree of proton transfer within the hydrogen bond.

Phys Chem Chem Phys ; 24(13): 7882-7892, 2022 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-35302575


Triphenylpnictogens were oxidized to access diphenylpnictioginic acids Ph2XOOH (X = P, As, Sb, Bi). It was shown that oxidation with chloramine-T does not lead to the cleavage of a C-pnictogen bond. The preliminary reductive cleavage with sodium in liquid ammonia followed by the oxidation with hydrogen peroxide was successfully utilised for the synthesis of diphenylphosphinic and diphenylarsinic acids. It was shown that in solid state (by means of XRD), all diphenylpnictoginic acids form polymeric chains. Diphenylbismuthinic and diphenylantimonic acids form polymeric covalent adducts, while diphenylphosphinic and diphenylarsinic chains are associated through hydrogen bonding. Unlike diphenylphosphinic acid, diphenilarsinic acid forms two polymorphs of hydrogen-bonded infinite chains. In solution in a polar aprotic solvent diphenylarsinic acid, similarly to dimethylarsinic, forms hydrogen-bonded cyclic dimers together with a small amount of cyclic trimers.

Hidrogênio , Polímeros , Ligação de Hidrogênio , Solventes
ACS Nano ; 14(7): 9059-9065, 2020 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-32628444


Chalcogenide phase-change materials show strikingly contrasting optical and electrical properties, which has led to their extensive implementation in various memory devices. By performing spin-, time-, and angle-resolved photoemission spectroscopy combined with the first-principles calculation, we report the experimental results that the crystalline phase of GeSb2Te4 is topologically nontrivial in the vicinity of the Dirac semimetal phase. The resulting linearly dispersive bulk Dirac-like bands that cross the Fermi level and are thus responsible for conductivity in the stable crystalline phase of GeSb2Te4 can be viewed as a 3D analogue of graphene. Our finding provides us with the possibility of realizing inertia-free Dirac currents in phase-change materials.