24 research outputs found
New 1D and 2D Nanoscaled Materials Based on the Tetraoxa[8]circulene Monomer
New one- and two-dimensional p-conjugated materials containing a tetraoxa[8]circulene monomer are theoretically predicted on the basis of density functional theory techniques. These novel materials are predicted to demonstrate a promising hole/electron mobility properties which are typical for the ambipolar organic semiconductors. Furthermore, the growth of p-conjugation determines the strong visible light absorption of the studied systems in a great contrast to the initial lack of color of the tetraoxa[8]circulene compound. The synthesis of these new organic p-conjugated materials is an important task because of their potential practical applications in optoelectronic devices
Possible electronic mechanisms of generation and quenching of luminescence of singlet oxygen in the course of photodynamic therapy: ab initio study
On the basis of ab initio quantum chemical calculations the strong enhancement of the ΒΉ(a1ΞgΒ·Sβ)β ΒΉ(XΒ³Ξ£gβ Β·T) transition in collision complex between Oβ and organic dye is predicted, where T is the triplet excited state of the dye and Sβ is its ground singlet state. The collision-induced electric dipole transition moment depends on polarizability of the dye and can be used for the estimation of energy transfer rate constant. Quantum chemical calculations can predict the most efficient dye sensibilizer for photodynamic therapy of cancer, instead of the difficult experimental search. Some new ideas are proposed for additional laser simulated mechanisms of active oxygen generation.ΠΠ° ΠΎΡΠ½ΠΎΠ²Ρ ab initio ΠΊΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΡΠΌΡΡΠ½ΠΈΡ
ΡΠΎΠ·ΡΠ°Ρ
ΡΠ½ΠΊΡΠ² ΠΏΠ΅ΡΠ΅Π΄Π±Π°ΡΠ΅Π½ΠΎ ΡΡΡΠΎΡΠ½Π΅ Π·ΡΠΎΡΡΠ°Π½Π½Ρ ΒΉ(a1ΞgΒ·Sβ)β ΒΉ(XΒ³Ξ£gβ Β·T) ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Ρ Π² ΠΊΠΎΠΌΠΏΒΠ»Π΅ΠΊΡΡ Π·ΡΡΠΊΠ½Π΅Π½Π½Ρ Oβ Π· ΠΎΡΠ³Π°Π½ΡΡΠ½ΠΈΠΌ Π±Π°ΡΠ²Π½ΠΈΠΊΠΎΠΌ, Π΄Π΅ Π’ β ΡΠ΅ ΡΡΠΈΠΏΒΠ»Π΅ΡΠ½ΠΈΠΉ Π·Π±ΡΠ΄ΠΆΠ΅Π½ΠΈΠΉ, a Sβ β ΠΎΡΠ½ΠΎΠ²Π½ΠΈΠΉ ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΈΠΉ ΡΡΠ°Π½ Π±Π°ΡΠ²Π½ΠΈΠΊΠ°. ΠΠ½Π΄ΡΠΊΠΎΠ²Π°Π½ΠΈΠΉ Π·ΡΡΠΊΠ½Π΅Π½Π½ΡΠΌ Π΅Π»Π΅ΠΊΡΡΠΎΠ΄ΠΈΠΏΠΎΠ»ΡΠ½ΠΈΠΉ ΠΌΠΎΠΌΠ΅Π½Ρ ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Ρ Π·Π°Π»Π΅ΠΆΠΈΡΡ Π²ΡΠ΄ ΠΏΠΎΠ»ΡΡΠΈΠ·ΠΎΠ²Π°Π½ΠΎΡΡΡ Π±Π°ΡΠ²Π½ΠΈΠΊΠ° Ρ ΠΌΠΎΠΆΠ΅ Π±ΡΡΠΈ Π²ΠΈΠΊΠΎΡΠΈΒΡΡΠ°Π½ΠΈΠΉ Π΄Π»Ρ ΠΎΡΡΠ½ΠΊΠΈ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ ΠΏΠ΅ΡΠ΅Π½Π΅ΡΠ΅Π½Π½Ρ Π΅Π½Π΅ΡΠ³ΡΡ. ΠΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΡΠΌΡΡΠ½ΠΈΠΌΠΈ ΡΠΎΠ·ΡΠ°Ρ
ΡΠ½ΠΊΠ°ΠΌΠΈ ΠΌΠΎΠΆΠ½Π° ΡΠΎΡΠ½ΡΡΠ΅ ΠΏΠ΅ΡΠ΅Π΄Π±Π°ΡΠΈΡΠΈ Π½Π°ΠΉΠ΅ΒΡΠ΅ΠΊΡΠΈΠ²Π½ΡΡΠΈΠΉ Π±Π°ΡΠ²Π½ΠΈΠΊ-ΡΠ΅Π½ΡΠΈΠ±ΡΠ»ΡΠ·Π°ΡΠΎΡ Π΄Π»Ρ ΡΠΎΡΠΎΠ΄ΠΈΠ½Π°ΠΌΡΡΠ½ΠΎΡ ΡΠ΅ΒΡΠ°ΠΏΡΡ ΡΠ°ΠΊΠ°, Π½ΡΠΆ ΡΠΊΠ»Π°Π΄Π½ΠΈΠΌΠΈ Π΅ΠΊΡΠΏΠ΅ΡΠΈΠΌΠ΅Π½ΡΠ°Π»ΡΠ½ΠΈΠΌΠΈ Π΄ΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½ΒΠ½ΡΠΌΠΈ. ΠΠ°ΠΏΡΠΎΠΏΠΎΠ½ΠΎΠ²Π°Π½ΠΎ Π΄Π΅ΡΠΊΡ Π½ΠΎΠ²Ρ ΡΠ΄Π΅Ρ ΡΡΠΎΡΠΎΠ²Π½ΠΎ ΠΌΠ΅Ρ
Π°Π½ΡΠ·ΠΌΡΠ² Π΄ΠΎΒΠ΄Π°ΡΠΊΠΎΠ²ΠΎΠ³ΠΎ ΠΌΠΎΠ΄Π΅Π»ΡΠ²Π°Π½Π½Ρ ΡΡΠ°Π΄ΡΡ Π°ΠΊΡΠΈΠ²Π°ΡΡΡ ΠΊΠΈΡΠ½Ρ.ΠΠ° ΠΎΡΠ½ΠΎΠ²Π°Π½ΠΈΠΈ ab initio ΠΊΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ°ΡΡΠ΅ΡΠΎΠ² ΠΏΡΠ΅Π΄ΡΠΊΠ°ΒΠ·Π°Π½ΠΎ ΡΠΈΠ»ΡΠ½ΠΎΠ΅ ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΠ΅ ΒΉ(a1ΞgΒ·Sβ)β ΒΉ(XΒ³Ξ£gβ Β·T) ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Π° Π² ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ΅ ΡΡΠΎΠ»ΠΊΠ½ΠΎΠ²Π΅Π½ΠΈΡ Oβ Ρ ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΠΌ ΠΊΡΠ°ΡΠΈΡΠ΅Π»Π΅ΠΌ, Π³Π΄Π΅ Π’ β ΡΡΠΈΠΏΠ»Π΅ΡΠ½ΠΎΠ΅ Π²ΠΎΠ·Π±ΡΠΆΠ΄Π΅Π½Π½ΠΎΠ΅, a Sβ β ΠΎΡΠ½ΠΎΠ²Π½ΠΎΠ΅ ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΎΠ΅ ΡΠΎΡΡΠΎΡΠ½ΠΈΠ΅ ΠΊΡΠ°ΡΠΈΡΠ΅Π»Ρ. ΠΠ½Π΄ΡΡΠΈΡΠΎΠ²Π°Π½Π½ΡΠΉ ΡΡΠΎΠ»ΠΊΠ½ΠΎΠ²Π΅Π½ΠΈΠ΅ΠΌ ΡΠ»Π΅ΠΊΡΡΠΎΠ΄ΠΈΠΏΠΎΠ»ΡΠ½ΡΠΉ ΠΌΠΎΠΌΠ΅Π½Ρ ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Π° Π·Π°Π²ΠΈΡΠΈΡ ΠΎΡ ΠΏΠΎΠ»ΡΡΠΈΠ·ΡΠ΅ΠΌΠΎΡΡΠΈ ΠΊΡΠ°ΡΠΈΡΠ΅Π»Ρ ΠΈ ΠΌΠΎΠΆΠ΅Ρ Π±ΡΡΡ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ Π΄Π»Ρ ΠΎΡΠ΅Π½ΠΊΠΈ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ ΠΏΠ΅ΡΠ΅Π½ΠΎΡΠ° ΡΠ½Π΅ΡΠ³ΠΈΠΈ. ΠΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΠΌΠΈ ΡΠ°ΡΡΠ΅ΡΠ°ΠΌΠΈ ΠΌΠΎΠΆΠ½ΠΎ ΡΠΎΡΠ½Π΅Π΅ ΠΏΡΠ΅Π΄ΡΠΊΠ°Π·Π°ΡΡ Π½Π°ΠΈΠ±ΠΎΠ»Π΅Π΅ ΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΡΠΉ ΠΊΡΠ°ΡΠΈΡΠ΅Π»Ρ-ΡΠ΅Π½ΡΠΈΒΠ±ΠΈΠ»ΠΈΠ·Π°ΡΠΎΡ Π΄Π»Ρ ΡΠΎΡΠΎΠ΄ΠΈΠ½Π°ΠΌΠΈΡΠ΅ΡΠΊΠΎΠΉ ΡΠ΅ΡΠ°ΠΏΠΈΠΈ ΡΠ°ΠΊΠ°, Π½Π΅ΠΆΠ΅Π»ΠΈ ΡΠ»ΠΎΠΆΒΠ½ΡΠΌΠΈ ΡΠΊΡΠΏΠ΅ΡΠΈΠΌΠ΅Π½ΡΠ°Π»ΡΠ½ΡΠΌΠΈ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΈΡΠΌΠΈ. ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½Ρ Π½Π΅ΠΊΠΎΒΡΠΎΡΡΠ΅ Π½ΠΎΠ²ΡΠ΅ ΠΈΠ΄Π΅ΠΈ ΠΎΡΠ½ΠΎΡΠΈΡΠ΅Π»ΡΠ½ΠΎ ΠΌΠ΅Ρ
Π°Π½ΠΈΠ·ΠΌΠΎΠ² Π΄ΠΎΠΏΠΎΠ»Π½ΠΈΡΠ΅Π»ΡΠ½ΠΎΠ³ΠΎ ΠΌΠΎΠ΄Π΅Π»ΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΡΡΠ°Π΄ΠΈΠΈ Π°ΠΊΡΠΈΠ²Π°ΡΠΈΠΈ ΠΊΠΈΡΠ»ΠΎΡΠΎΠ΄
Spin-dependent binding of dioxygen to heme and charge-transfer mechanism of spin-orbit coupling enhancement
Spin-orbit coupling (SOC) between the starting triplet Β³A''(2) state from the entrance channel of the heme-O2 binding reaction and the final singlet ΒΉA'(1) open-shell state, which are dominated by the Fe^3+-O2-radical-pair structures, is studied. Simulated potential energy surface cross sections along the reaction coordinate for these and other multiplets, calculated by density functional theory (DFT) agree with the recent DFT studies known from the literature. The heme-model includes Fe(II)-porphyrin complex with imidazol, or ammonia molecule, at the fith coordination position, which simulates the hystidine as an aminoacide residue of myoglobin. The SOC is induced mainly at the oxygen moiety by an orbital angular momentum change in the Ο8-shell during the triplet-singlet transition. This SOC model explains pretty well the efficient spin inversion during the heme-O2 binding.ΠΠΈΠ²ΡΠ΅Π½ΠΎ ΡΠΏΡΠ½-ΠΎΡΠ±ΡΡΠ°Π»ΡΠ½Ρ Π²Π·Π°ΡΠΌΠΎΠ΄ΡΡ (Π‘ΠΠ) ΠΌΡΠΆ ΠΏΠΎΡΠ°ΡΠΊΠΎΠ²ΠΈΠΌ ΡΡΠΈΠΏΠ»Π΅ΡΠ½ΠΈΠΌ Β³Π''(2) ΡΡΠ°Π½ΠΎΠΌ Ρ Π²Ρ
ΡΠ΄Π½ΠΎΠΌΡ ΠΊΠ°Π½Π°Π»Ρ ΡΠ΅Π°ΠΊΡΡΡ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ Π³Π΅ΠΌ-Π2 Ρ ΠΊΡΠ½ΡΠ΅Π²ΠΈΠΌ ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΈΠΌ ΒΉΠ'(1) ΡΡΠ°Π½ΠΎΠΌ Π· Π²ΡΠ΄ΠΊΡΠΈΡΠΎΡ ΠΎΠ±ΠΎΠ»ΠΎΠ½ΠΊΠΎΡ, ΡΠΊΡ Π²ΠΈΠ·Π½Π°ΡΠ΅Π½Ρ Π΄ΠΎΠΌΡΠ½ΡΠ²Π°Π»ΡΠ½ΠΈΠΌ Π²ΠΊΠ»Π°Π΄ΠΎΠΌ ΡΡΡΡΠΊΡΡΡΠΈ ΡΠ°Π΄ΠΈΠΊΠ°Π»ΡΠ½ΠΎΡ ΠΏΠ°ΡΠΈ Fe^3+-O2-. ΠΠ΅ΡΠ΅ΡΠΈΠ½ΠΈ ΠΌΠΎΠ΄Π΅Π»ΡΠ½ΠΈΡ
ΠΏΠΎΠ²Π΅ΡΡ
ΠΎΠ½Ρ ΠΏΠΎΡΠ΅Π½ΡΡΠ°Π»ΡΠ½ΠΎΡ Π΅Π½Π΅ΡΠ³ΡΡ Π²Π·Π΄ΠΎΠ²ΠΆ ΠΊΠΎΠΎΡΠ΄ΠΈΠ½Π°ΡΠΈ ΡΠ΅Π°ΠΊΡΡΡ Π΄Π»Ρ ΡΠΈΡ
ΠΌΡΠ»ΡΡΠΈΠΏΠ»Π΅ΡΡΠ², ΡΠΎΠ·ΡΠ°Ρ
ΠΎΠ²Π°Π½Ρ Π·Π° ΡΠ΅ΠΎΡΡΡΡ ΡΡΠ½ΠΊΡΡΠΎΠ½Π°Π»Ρ Π³ΡΡΡΠΈΠ½ΠΈ (Π’Π€Π), ΡΠ·Π³ΠΎΠ΄ΠΆΡΡΡΡΡΡ Π· Π½Π΅Π΄Π°Π²Π½ΡΠΌΠΈ ΡΠΎΠ·ΡΠ°Ρ
ΡΠ½ΠΊΠ°ΠΌΠΈ Π’Π€Π, Π²ΡΠ΄ΠΎΠΌΠΈΠΌΠΈ Π· Π»ΡΡΠ΅ΡΠ°ΡΡΡΠΈ. ΠΠΎΠ΄Π΅Π»Ρ Π³Π΅ΠΌΠ° Π²ΠΊΠ»ΡΡΠ°Ρ Fe(II)-ΠΏΠΎΡΡΡΠ½, ΠΊΠΎΠΎΡΠ΄ΠΈΠ½ΠΎΠ²Π°Π½ΠΈΠΉ Π· ΡΠΌΡΠ΄Π°Π·ΠΎΠ»ΠΎΠΌ Π°Π±ΠΎ Π°ΠΌΠΎΠ½ΡΠ°ΠΊΠΎΠΌ Ρ ΠΏβΡΡΡΠΉ ΠΊΠΎΠΎΡΠ΄ΠΈΠ½Π°ΡΡΠΉΠ½ΡΠΉ ΠΏΠΎΠ·ΠΈΡΡΡ ΠΉΠΎΠ½Π° Π·Π°Π»ΡΠ·Π°, ΡΠΊΡ ΠΌΠΎΠ΄Π΅Π»ΡΡΡΡ Π³ΡΡΡΠΈΠ΄ΠΈΠ½ ΡΠΊ Π°ΠΌΡΠ½ΠΎΠΊΠΈΡΠ»ΠΎΡΠ½ΠΈΠΉ Π·Π°Π»ΠΈΡΠΎΠΊ ΠΌΡΠΎΠ³Π»ΠΎΠ±ΡΠ½Ρ. Π‘ΠΠ ΡΠ½Π΄ΡΠΊΡΡΡΡΡΡ Π³ΠΎΠ»ΠΎΠ²Π½ΠΈΠΌ ΡΠΈΠ½ΠΎΠΌ Π½Π° ΠΊΠΈΡΠ½Ρ Π·Π° ΡΠ°Ρ
ΡΠ½ΠΎΠΊ Π·ΠΌΡΠ½ΠΈ ΠΎΡΠ±ΡΡΠ°Π»ΡΠ½ΠΎΠ³ΠΎ ΠΊΡΡΠΎΠ²ΠΎΠ³ΠΎ ΠΌΠΎΠΌΠ΅Π½ΡΡ Οg-ΠΎΠ±ΠΎΠ»ΠΎΠ½ΠΊΠΈ ΠΏΡΠΈ ΡΡΠΈΠΏΠ»Π΅Ρ-ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΎΠΌΡ ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Ρ. Π¦Ρ ΠΌΠΎΠ΄Π΅Π»Ρ Π‘ΠΠ Π΄ΠΎΠ±ΡΠ΅ ΠΏΠΎΡΡΠ½ΡΡ Π΅ΡΠ΅ΠΊΡΠΈΠ²Π½Ρ ΡΠ½Π²Π΅ΡΡΡΡ ΡΠΏΡΠ½Ρ Π² Ρ
ΠΎΠ΄Ρ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ Π³Π΅ΠΌ-Π2
New 1D and 2D Nanoscaled Materials Based on the Tetraoxa[8]circulene Monomer
New one- and two-dimensional p-conjugated materials containing a tetraoxa[8]circulene monomer are theoretically predicted on the basis of density functional theory techniques. These novel materials are predicted to demonstrate a promising hole/electron mobility properties which are typical for the ambipolar organic semiconductors. Furthermore, the growth of p-conjugation determines the strong visible light absorption of the studied systems in a great contrast to the initial lack of color of the tetraoxa[8]circulene compound. The synthesis of these new organic p-conjugated materials is an important task because of their potential practical applications in optoelectronic devices
Tight-binding g-Factor Calculations of CdSe Nanostructures
The Lande g-factors for CdSe quantum dots and rods are investigated within
the framework of the semiempirical tight-binding method. We describe methods
for treating both the n-doped and neutral nanostructures, and then apply these
to a selection of nanocrystals of variable size and shape, focusing on
approximately spherical dots and rods of differing aspect ratio. For the
negatively charged n-doped systems, we observe that the g-factors for
near-spherical CdSe dots are approximately independent of size, but show strong
shape dependence as one axis of the quantum dot is extended to form rod-like
structures. In particular, there is a discontinuity in the magnitude of
g-factor and a transition from anisotropic to isotropic g-factor tensor at
aspect ratio ~1.3. For the neutral systems, we analyze the electron g-factor of
both the conduction and valence band electrons. We find that the behavior of
the electron g-factor in the neutral nanocrystals is generally similar to that
in the n-doped case, showing the same strong shape dependence and discontinuity
in magnitude and anisotropy. In smaller systems the g-factor value is dependent
on the details of the surface model. Comparison with recent measurements of
g-factors for CdSe nanocrystals suggests that the shape dependent transition
may be responsible for the observations of anomalous numbers of g-factors at
certain nanocrystal sizes.Comment: 15 pages, 6 figures. Fixed typos to match published versio
Possible electronic mechanisms of generation and quenching of luminescence of singlet oxygen in the course of photodynamic therapy: ab initio study
On the basis of ab initio quantum chemical calculations the strong enhancement of the ΒΉ(a1ΞgΒ·Sβ)β ΒΉ(XΒ³Ξ£gβ Β·T) transition in collision complex between Oβ and organic dye is predicted, where T is the triplet excited state of the dye and Sβ is its ground singlet state. The collision-induced electric dipole transition moment depends on polarizability of the dye and can be used for the estimation of energy transfer rate constant. Quantum chemical calculations can predict the most efficient dye sensibilizer for photodynamic therapy of cancer, instead of the difficult experimental search. Some new ideas are proposed for additional laser simulated mechanisms of active oxygen generation.ΠΠ° ΠΎΡΠ½ΠΎΠ²Ρ ab initio ΠΊΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΡΠΌΡΡΠ½ΠΈΡ
ΡΠΎΠ·ΡΠ°Ρ
ΡΠ½ΠΊΡΠ² ΠΏΠ΅ΡΠ΅Π΄Π±Π°ΡΠ΅Π½ΠΎ ΡΡΡΠΎΡΠ½Π΅ Π·ΡΠΎΡΡΠ°Π½Π½Ρ ΒΉ(a1ΞgΒ·Sβ)β ΒΉ(XΒ³Ξ£gβ Β·T) ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Ρ Π² ΠΊΠΎΠΌΠΏΒΠ»Π΅ΠΊΡΡ Π·ΡΡΠΊΠ½Π΅Π½Π½Ρ Oβ Π· ΠΎΡΠ³Π°Π½ΡΡΠ½ΠΈΠΌ Π±Π°ΡΠ²Π½ΠΈΠΊΠΎΠΌ, Π΄Π΅ Π’ β ΡΠ΅ ΡΡΠΈΠΏΒΠ»Π΅ΡΠ½ΠΈΠΉ Π·Π±ΡΠ΄ΠΆΠ΅Π½ΠΈΠΉ, a Sβ β ΠΎΡΠ½ΠΎΠ²Π½ΠΈΠΉ ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΈΠΉ ΡΡΠ°Π½ Π±Π°ΡΠ²Π½ΠΈΠΊΠ°. ΠΠ½Π΄ΡΠΊΠΎΠ²Π°Π½ΠΈΠΉ Π·ΡΡΠΊΠ½Π΅Π½Π½ΡΠΌ Π΅Π»Π΅ΠΊΡΡΠΎΠ΄ΠΈΠΏΠΎΠ»ΡΠ½ΠΈΠΉ ΠΌΠΎΠΌΠ΅Π½Ρ ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Ρ Π·Π°Π»Π΅ΠΆΠΈΡΡ Π²ΡΠ΄ ΠΏΠΎΠ»ΡΡΠΈΠ·ΠΎΠ²Π°Π½ΠΎΡΡΡ Π±Π°ΡΠ²Π½ΠΈΠΊΠ° Ρ ΠΌΠΎΠΆΠ΅ Π±ΡΡΠΈ Π²ΠΈΠΊΠΎΡΠΈΒΡΡΠ°Π½ΠΈΠΉ Π΄Π»Ρ ΠΎΡΡΠ½ΠΊΠΈ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ ΠΏΠ΅ΡΠ΅Π½Π΅ΡΠ΅Π½Π½Ρ Π΅Π½Π΅ΡΠ³ΡΡ. ΠΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΡΠΌΡΡΠ½ΠΈΠΌΠΈ ΡΠΎΠ·ΡΠ°Ρ
ΡΠ½ΠΊΠ°ΠΌΠΈ ΠΌΠΎΠΆΠ½Π° ΡΠΎΡΠ½ΡΡΠ΅ ΠΏΠ΅ΡΠ΅Π΄Π±Π°ΡΠΈΡΠΈ Π½Π°ΠΉΠ΅ΒΡΠ΅ΠΊΡΠΈΠ²Π½ΡΡΠΈΠΉ Π±Π°ΡΠ²Π½ΠΈΠΊ-ΡΠ΅Π½ΡΠΈΠ±ΡΠ»ΡΠ·Π°ΡΠΎΡ Π΄Π»Ρ ΡΠΎΡΠΎΠ΄ΠΈΠ½Π°ΠΌΡΡΠ½ΠΎΡ ΡΠ΅ΒΡΠ°ΠΏΡΡ ΡΠ°ΠΊΠ°, Π½ΡΠΆ ΡΠΊΠ»Π°Π΄Π½ΠΈΠΌΠΈ Π΅ΠΊΡΠΏΠ΅ΡΠΈΠΌΠ΅Π½ΡΠ°Π»ΡΠ½ΠΈΠΌΠΈ Π΄ΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½ΒΠ½ΡΠΌΠΈ. ΠΠ°ΠΏΡΠΎΠΏΠΎΠ½ΠΎΠ²Π°Π½ΠΎ Π΄Π΅ΡΠΊΡ Π½ΠΎΠ²Ρ ΡΠ΄Π΅Ρ ΡΡΠΎΡΠΎΠ²Π½ΠΎ ΠΌΠ΅Ρ
Π°Π½ΡΠ·ΠΌΡΠ² Π΄ΠΎΒΠ΄Π°ΡΠΊΠΎΠ²ΠΎΠ³ΠΎ ΠΌΠΎΠ΄Π΅Π»ΡΠ²Π°Π½Π½Ρ ΡΡΠ°Π΄ΡΡ Π°ΠΊΡΠΈΠ²Π°ΡΡΡ ΠΊΠΈΡΠ½Ρ.ΠΠ° ΠΎΡΠ½ΠΎΠ²Π°Π½ΠΈΠΈ ab initio ΠΊΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ°ΡΡΠ΅ΡΠΎΠ² ΠΏΡΠ΅Π΄ΡΠΊΠ°ΒΠ·Π°Π½ΠΎ ΡΠΈΠ»ΡΠ½ΠΎΠ΅ ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΠ΅ ΒΉ(a1ΞgΒ·Sβ)β ΒΉ(XΒ³Ξ£gβ Β·T) ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Π° Π² ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠ΅ ΡΡΠΎΠ»ΠΊΠ½ΠΎΠ²Π΅Π½ΠΈΡ Oβ Ρ ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΠΌ ΠΊΡΠ°ΡΠΈΡΠ΅Π»Π΅ΠΌ, Π³Π΄Π΅ Π’ β ΡΡΠΈΠΏΠ»Π΅ΡΠ½ΠΎΠ΅ Π²ΠΎΠ·Π±ΡΠΆΠ΄Π΅Π½Π½ΠΎΠ΅, a Sβ β ΠΎΡΠ½ΠΎΠ²Π½ΠΎΠ΅ ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΎΠ΅ ΡΠΎΡΡΠΎΡΠ½ΠΈΠ΅ ΠΊΡΠ°ΡΠΈΡΠ΅Π»Ρ. ΠΠ½Π΄ΡΡΠΈΡΠΎΠ²Π°Π½Π½ΡΠΉ ΡΡΠΎΠ»ΠΊΠ½ΠΎΠ²Π΅Π½ΠΈΠ΅ΠΌ ΡΠ»Π΅ΠΊΡΡΠΎΠ΄ΠΈΠΏΠΎΠ»ΡΠ½ΡΠΉ ΠΌΠΎΠΌΠ΅Π½Ρ ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄Π° Π·Π°Π²ΠΈΡΠΈΡ ΠΎΡ ΠΏΠΎΠ»ΡΡΠΈΠ·ΡΠ΅ΠΌΠΎΡΡΠΈ ΠΊΡΠ°ΡΠΈΡΠ΅Π»Ρ ΠΈ ΠΌΠΎΠΆΠ΅Ρ Π±ΡΡΡ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ Π΄Π»Ρ ΠΎΡΠ΅Π½ΠΊΠΈ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ ΠΏΠ΅ΡΠ΅Π½ΠΎΡΠ° ΡΠ½Π΅ΡΠ³ΠΈΠΈ. ΠΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΠΌΠΈ ΡΠ°ΡΡΠ΅ΡΠ°ΠΌΠΈ ΠΌΠΎΠΆΠ½ΠΎ ΡΠΎΡΠ½Π΅Π΅ ΠΏΡΠ΅Π΄ΡΠΊΠ°Π·Π°ΡΡ Π½Π°ΠΈΠ±ΠΎΠ»Π΅Π΅ ΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΡΠΉ ΠΊΡΠ°ΡΠΈΡΠ΅Π»Ρ-ΡΠ΅Π½ΡΠΈΒΠ±ΠΈΠ»ΠΈΠ·Π°ΡΠΎΡ Π΄Π»Ρ ΡΠΎΡΠΎΠ΄ΠΈΠ½Π°ΠΌΠΈΡΠ΅ΡΠΊΠΎΠΉ ΡΠ΅ΡΠ°ΠΏΠΈΠΈ ΡΠ°ΠΊΠ°, Π½Π΅ΠΆΠ΅Π»ΠΈ ΡΠ»ΠΎΠΆΒΠ½ΡΠΌΠΈ ΡΠΊΡΠΏΠ΅ΡΠΈΠΌΠ΅Π½ΡΠ°Π»ΡΠ½ΡΠΌΠΈ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΈΡΠΌΠΈ. ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½Ρ Π½Π΅ΠΊΠΎΒΡΠΎΡΡΠ΅ Π½ΠΎΠ²ΡΠ΅ ΠΈΠ΄Π΅ΠΈ ΠΎΡΠ½ΠΎΡΠΈΡΠ΅Π»ΡΠ½ΠΎ ΠΌΠ΅Ρ
Π°Π½ΠΈΠ·ΠΌΠΎΠ² Π΄ΠΎΠΏΠΎΠ»Π½ΠΈΡΠ΅Π»ΡΠ½ΠΎΠ³ΠΎ ΠΌΠΎΠ΄Π΅Π»ΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΡΡΠ°Π΄ΠΈΠΈ Π°ΠΊΡΠΈΠ²Π°ΡΠΈΠΈ ΠΊΠΈΡΠ»ΠΎΡΠΎΠ΄
Electrocatalytic Properties of Fe-Cu Composites Prepared on the Basis of the Reduced Copper (II) Ferrite
Copper ferrite (CuFe2O4) samples were prepared by the co-precipitation method without and in the presence of a polymer stabilizer (polyvinyl alcohol, PVA) followed by heat treatment at 500, 700, and 900Β°C and electrochemical reduction. The structure and morphological features of the samples were investigated by X-ray phase analysis and electron microscopy. It was established that copper (II) ferrite is reduced in an electrochemical system with the formation of Fe-Cu composites with different content of reduced metals, which is influenced by the heat treatment temperature. Copper ferrite prepared with the use of the polymer stabilizer is partially reduced during thermolysis, additionally in an electrochemical cell. The Fe-Cu composites were employed as electrocatalysts in the electrohydrogenation of p-nitrobenzoic acid and exhibited good activity in this process. To study the interaction in the CuFe2O4 + PVA complexes, the quantum-chemical calculations were performed using the density functional theory methods for the simplified metal-containing systems (atoms and ions of copper (II), iron (III), Cu2, Fe2 molecules) as well as dimers and trimers modeling the structure of polyvinyl alcohol