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Phys Chem Chem Phys ; 21(30): 16751-16761, 2019 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-31322638


In the context of the decisive role that vibronic interactions play in the functioning of molecular quantum cellular automata, in this article we give a comparative analysis of the two alternative vibronic approaches to the evaluation of the key functional characteristics of molecular cells. Semiclassical Born-Oppenheimer approximation and quantum mechanical evaluations of the vibronic energy pattern, electronic density distributions and cell-cell response function are performed for two-electron square-planar mixed valence molecular cells subjected to the action of a molecular driver. Special emphasis is put on the description of the cell-cell response function, which describes strong non-linearity as a prerequisite for the effective action of quantum cellular automata. Comparison of results obtained within the semiclassical and quantum-mechanical approaches has revealed a drastic difference between the shapes of the cell-cell response functions evaluated within these two approaches in the case of moderate vibronic coupling when the energy levels of the square cell interacting with a weakly polarized driver undergo large tunneling splitting in shallow adiabatic potential minima. In contrast, in the limits of strong vibronic coupling (a double-well adiabatic potential with deep minima) and weak vibronic coupling (a single well adiabatic potential) the adiabatic approximation is shown to describe the cell-cell response function with rather good accuracy.

Nanotecnologia/métodos , Teoria Quântica , Nanotecnologia/instrumentação , Vibração
J Phys Chem Lett ; 10(9): 2191-2195, 2019 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-30978026


An effect of deblocking of small size (8R, D8R) pores in zeolites due to cation drift is analyzed by using ab initio molecular dynamics (AIMD) at the PBE-D2/PAW level. The effect of carbonate and hydrocarbonate species on the carbon dioxide uptake in NaKA zeolite is demonstrated. It is shown that a hydrocarbonate or carbonate anion can form strong complexes with K+ cation and withdraw it from the 8R window, so that the probability of CO2 diffusion through 8R increases. For the first time, correlations between cationic and HCO3-/CO32- positions are demonstrated in favor of their significant interaction leading to the cationic drift from 8R windows. This phenomenon explains a nonzero CO2 adsorption in narrow pore zeolites upon high Na/K exchange. In a gas mixture, such deblocking effect reduces the separation factor because of the possible passage of both components through the plane of partly open 8R windows.

J Mol Model ; 23(3): 68, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-28197839


The bulk and Young moduli and heats of hydration have been calculated at the DFT level for fully optimized models of all-siliceous and cationic zeolites with and without water, and then compared to the corresponding experimental data. Upon the addition of water, the monovalent alkali ion and divalent alkaline earth ion exchanged zeolites presented opposite trends in the elastic modulus. The main contribution to the decrease in the elastic modulus of the alkali ion exchanged zeolites appeared to be a shift of cations from the framework oxygen atoms upon water addition, with the coordination number often remaining the same. The contrasting increase in elastic modulus observed for the divalent (alkaline earth) ion exchanged zeolites was explained by cation stabilization resulting from increased coordination, which cannot be achieved within a rigid zeolite framework without water.

Inorg Chem ; 51(22): 12165-75, 2012 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-23131140


For bi- and trivalent Me(q+) (Me = metal) cations of alkaline earth (AE) and rare earth (RE) metals, respectively, the formation of the nonacid MeOH((q-1)+) species and acid H-Ozeo group, where Ozeo is the framework atom, from water adsorbed at the multivalent Me(q+)(H2O) cation in cationic form zeolites was checked at both isolated cluster (8R or 6R + 4R) and periodic (the mordenite framework) levels. Both approaches demonstrate qualitative differences for the stability of the dissociated water between the two classes of industrial cationic forms if two Al atoms are closely located. The RE forms split water while the AE ones do not, that can be a basis of different proton transfer in the RE zeolites (thermodynamic control) than in the AE forms (kinetic control). The cluster models allow quantitatively explaining nearly equal intensities IHF ∼ ILF of the high frequency (HF) and low frequency (LF) OH vibrations in the RE forms and lowered IHF ≪ ILF in the AE forms, where HF bands are assigned to the Me-OH groups in the RE and AE forms, respectively, while LF bands are assigned to the Si-O(H)-Al groups. The role of electrostatic terms for water dissociation in the RE and AE forms is discussed.