G.G. Devyatykh Institute of Chemistry of High-Purity Substances
Nizhny Novgorod | Russian Federation
Main Specialties: Chemistry
Additional Specialties: Physical Chemistry, Theoretical Chemistry
Work Experience: 2011: Research Assistant, Institute of Applied Physics, Russian Academy of Sciences
2013-2017: Senior Lecturer, Senior Teacher (in Russian “Starshii Prepodavatel”), Chair of Inorganic Chemistry, N.I. Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod
2012-present: Research Associate. Institute for Chemistry of High Purity Substances, Russian Academy of Sciences, Nizhny Novgorod
Primary Affiliation: G.G. Devyatykh Institute of Chemistry of High-Purity Substances - Nizhny Novgorod , Russian Federation
10PubMed Central Citations
Catal. Sci. Technol., 2019,9, 3398-3407
Catalysis Science & Technology
NHC-supported trihydrides Cp(NHC)RuH3 show excellent catalytic activity in the H/D exchange of pyridine and some other N-heterocycles under mild conditions and low catalyst loading. Of the catalysts screened, Cp(IMes)RuH3 showed the highest activity. H/D exchange in other aromatic systems also occurs with good to excellent conversions, whereas aliphatic, olefinic and acetylenic positions are much less active. This result is complementary to the significant aliphatic H/D exchange mediated by the related complex Cp(iPr3P)RuH3 (1). Mechanistic studies, supported by DFT calculations, suggest that the reaction proceeds via elimination of dihydrogen from Cp(NHC)RuH3 to give the monohydride Cp(NHC)RuH amenable to oxidative addition of C–H for aromatic (benzene and pyridine) and aliphatic (methane and ethane) substrates. Different reaction paths were revealed: a two-step route with an intermediate, a single step with a pre-reactive complex, and a reaction path branching with a bifurcation point. For pyridine, DFT calculations show that the catalyst off-loop state Cp(L)RuH(py) is less stable relative to Cp(L)RuH in the case of L = NHC than for L = iPr3P, ΔrG(50 °C) = 2.6 kcal mol−1vs. −9.41 kcal mol−1, respectively, which may account for the difference in reactivity of these two catalytic systems. The DFT results for the B3LYP, M06L, and SCAN functionals were benchmarked against each other and the DLPNO-CCSD(T) and DLPNO-MP2 data and discussed with respect to the determined catalytic activity and the catalyst inhibition.
The quantum chemical study of the MeOOH/(MeO)3Al model system has been carried out in order to predict the mechanism of the catalytic decomposition of t-BuOOH under mild conditions for the t-BuOOH/(t-BuO)3Al system being a powerful synthetic tool for selective oxidation. To elucidate chemical excitation of O2 eliminated in the catalytic reaction and to predict electronic state of O2, the topology of the potential energy surface (PES), the structures of intermediates and transition states, the activation and reaction energies were obtained at the B3LYP/cc-pVTZ theory level. It was shown that the peroxide, (MeO)2AlOOMe, corresponding to the experimentally obtained (t-BuO)2AlOOBu-t, is formed in the first step of the reaction. After that, in the main pathway, the aluminum-containing peroxide reacts with the second МeOOH molecule through the nucleophilic substitution of the second methoxy group forming the MeOAl(OOMe)2 diperoxide. The diperoxide rearranges to aluminum-containing ozonide MeOAlOOOMe. The ozonide isomerizes in the mononuclear-metal dioxygen intermediate (MeO)3Al•O2. The latter decomposes through the adiabatic ((MeO)3Al+O2(b1Σg )) and non-adiabatic ((MeO)3Al+O2(X3Σg )) pathways, which corresponds to experimental data about the incomplete conversion of O2 to O2( b1Σg). The generation of O2(b1Σg ) was revealed by the analysis of the energy diagram calculated with the CCSD(T), CCSDT(Q), and CASSCF methods. It was suggested that the ɳ1-(MeO)3Al•O2 and, thus, (t-BuO)3Al•O2 complexes are new sources of O2(b1Σg ).
J. Phys. Chem. C
Platinum and platinum based materials are of fundamental importance for modern and developed catalysts, fuel cells, sensors, hydrogen production and storage systems, nanoelectronic devices. The sub-nanosize cluster Pt24 was considered as a model of the prospective catalytic system based on the oxide and carbide supported Pt nanoparticles (Pt NPs) or Pt NPs with soft spacers anchored to their surface. Structural, electronic, thermodynamic and spectral properties of the adsorption complexes of molecular and atomic hydrogen on Pt NPs have been studied using the DFT method (BLYP functional with the 6-31G(p) basis for H and the CRENBS pseudopotential for Pt atoms). On this basis, the adsorption energies for molecular hydrogen at the Pt NP’s along with the energies and activation energies of its dissociation were estimated and the pathways of activationless dissociative adsorption were found. The full map of adsorption energies of atomic hydrogen at the various surface regions of Pt24 was obtained. The structures of transition states for the rearrangements between the adsorption complexes were located and the activation energies for surface migration were calculated. Additionally, several ways of subsurface diffusion of H atoms inside the Pt24 cluster were considered which allows estimating the diffusion parameters and the probability of the hydrogen spillover when the cluster surface is highly covered by ligands restricting the surface migration. The IR and Raman spectra of most favorable adsorption complexes were simulated to provide the possibility of an experimental validation of the results obtained.
J Mol Model 2014 Nov 15;20(11):2473. Epub 2014 Oct 15.
G.G. Devyatykh Institute of Chemistry of High-Purity Substances, Russian Academy of Sciences, 49 Troponina St., Nizhny Novgorod, 603950, Russia,
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J. Phys. Chem. C 2014, 118, 7398−7413
The Journal of Physical Chemistry C
The structures, energies, harmonic vibrational frequencies, and thermodynamic parameters of the water clusters (H2O)48, (H2O)72, and (H2O)270 were calculated using the standard DFT theory (BLYP/6-31++G(d,p) for small and medium clusters) and the modern tight-binding method SCC-DFTB (DFTBA and DFTB+). The adsorption and embedding of s-cis- and s-trans-glyoxal molecules as well as its sunlight UV photolysis products (molecules CH2O, HCOOH, H2O2, CO, CO2 and radicals CHO, HO, HO2) on nanosized ice clusters of up to 2.5 nm in diameter were studied within the above theoretical models. The structures of adsorption complexes on different sites of ice nanoparticles, the corresponding adsorption energies and thermodynamic parameters were estimated. We found that the DFTB method is a very promising tool for the calculations of structures and energies of ice nanoparticles, when compared to both DFT and semiempirical (PM3) methods. The obtained results are discussed in relation to the possible photolysis pathways, the reaction rates in the gas phase and in the adsorbed state, and the mechanisms of glyoxal photolysis catalyzed by the ice nanoparticles in the Earth’s atmosphere.
Cryst. Growth Des. 2013, 13, 1445−1457
Crystal Growth & Design
To elucidate an experimentally observed increase of GaN crystal growth rate in the Ga(l)-graphite-NH3(g) system (Jacobs, K. et al. J. Cryst. Growth 2010, 312, 750−755), a gas-phase chemical model of the chemical vapor deposition (CVD) process was developed in a quantum chemical study. The reaction mechanisms in a gas-phase Ga/HCN/NH3 system were predicted using density functional theory (DFT) and post-Hartree−Fock methods including conventional DFT (B3LYP/cc-pVTZ) and coupled cluster (CCSD/cc-pVTZ) theory levels. Activation and reaction energies were refined with a CCSD(T)/aug-cc-pVTZ//B3LYP/cc-pVTZ composite approach. A relatively modern variant of the coupled cluster theory (ROCCL method) in conjunction with the aug-cc-pVDZ basis set for H, N, and aug-cc-pV(D+d)Z for Ga atoms) was employed to investigate bond cleavage reaction pathways. Reactions in Ga(2P) + NH3 and Ga(2P) + HCN gas-phase systems and reactivity of products of the Ga(2P) + HCN reaction (HGaCN and HGaNC) with both Ga (atomic vapor) and NH3 (reactive diluent gas) were included in the model of the chemical transport. Elementary steps involving newly reported cyclic (HGaCNGa) containing intermediates were considered. The role of HCN as a chemical transport reagent in GaN CVD was established unambiguously. A comparative study of minimum energy pathways (MEPs) for reactions in the Ga/NH3 and Ga/HCN/NH3 systems supported the experimental observation of the GaN deposition rate increase.
J. Chem. Theory Comput. 2013, 9, 247−262
Journal of Chemical Theory and Computation
Recent experiments on the UV and electron beam irradiation of solid O2 reveals a series of IR features near the valence antisymmetric vibration band of O3 which are frequently interpreted as the formation of unusual On allotropes in the forms of weak complexes or covalently bound molecules. In order to elucidate the question of the nature of the irradiation products, the structure, relative energies, and vibrational frequencies of various forms of On (n = 1−6) in the singlet, triplet, and, in some cases, quintet states were studied using the CCSD(T) method up to the CCSD(T,full)/cc-pCVTZ and CCSD(T,FC)/aug-cc-pVTZ levels. The results of calculations demonstrate the existence of stable highly symmetric structures O4 (D3h), O4 (D2d), and O6 (D3d) as well as the intermolecular complexes O2·O2, O2·O3, and O3·O3 in different conformations. The calculations show that the local minimum corresponding to the O3···O complex is quite shallow and cannot explain the ν3 band features close to 1040 cm−1, as was proposed previously. For the ozone dimer, a new conformer was found which is more stable than the structure known to date. The effect of the ozone dimer on the registered IR spectra is discussed.
J Phys Chem A 2012 Oct 10;116(42):10420-34. Epub 2012 Oct 10.
Department of Chemistry, N.I. Lobachevsky State University of Nizhny Novgorod, National Research University, 23 Gagarin Avenue, Nizhny Novgorod 603950, Russia.
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J. Phys. Org. Chem. 2012, 25 971–978
Journal of Physical Organic Chemistry
The direct aldol reaction between acetone and 4-nitrobenzaldehyde catalyzed by sterically hindered L-prolinamide derivative (64 atoms) of the (11S,12S)-9,10-dihydro-9,10-ethanoanthracene-11,12-diamine molecule has been investigated using density functional theory at the B3LYP/6-31G(d) level of theory. The reliability of the B3LYP/6-31G(d) calculations to elucidate the reaction mechanism and estimate activation and reaction energies was confirmed by energy calculation of the net reaction with full geometry optimizations of the reactants and product at the B3LYP/6-311++G(2d,2p) as well as B2PLYP/def2-TZVPP levels with correction to Van der Waals interaction. The calculations reveal that the L-prolinamide derivative catalyzes the reaction according to a multistep enamine mechanism with highly activated C–C bond and/or enamine formation in the proposed mechanism. The final elementary reaction – the C–N bond cleavage in the chiral diol adduct – is accompanied by a very large barrier, which may inhibit further progression of the reaction. The origin of the enantioselectivity and the corresponding reaction paths to a chiral product were unambiguously identified.
J. Chem. Theory Comput. 2011, 7, 2021–2024
J. Chem. Theory Comput.
The reaction between molecular oxygen and two nitric oxide(II) molecules is studied with high-level ab initio wave function methods, including geometry optimizations with coupled cluster (CCSD(T,full)/cc-pCVTZ) and complete active space with second order perturbation theory levels (CASPT2/cc-pVDZ). The energy at the critical points was refined by calculations at the CCSD(T,full)/aug-cc-pCVTZ level. The controversies found in the previous theoretical studies are critically discussed and resolved. The best estimate of the activation energy is 6.47 kJ/mol.
J. Phys. Chem. C 2011, 115, 9081–9089
J. Phys. Chem. C
The low-temperature interaction between methyl hydroperoxide CH3OOH (MHP) and the hexagonal water ice surface was studied using DFT (BLYP/6-31þþG(d,p)) calculations. The structures, energies, and some thermodynamic properties of the molecular complexes between MHP and the water clusters (H2O)48, (H2O)56, (H2O)72 representing the surface fragments of the (0001), (10-10), and (11-20) crystallographic planes of the hexagonal oxygen lattice of the water ice Ih with proton ordering corresponding to Pisani’s P-ordered model were calculated. The various modes of coordination and intrusion were studied using the extended set (up to 192 points for each plane) of the structures optimized at the semiempirical (PM3) level. The validity of the surface models was verified by the stability of the results obtained in the cluster series (H2O)n, (n = 48, 72, 192, 216) at the semiempirical level as well as by DFT calculations of selected structures at the BLYP/6-311þþG(2d,2p) level.
J Phys Chem A 2009 Aug;113(32):9092-101
Department of Chemistry, N.I. Lobachevsky State University of Nizhny Novgorod, 23 Gagarin Avenue, Nizhny Novgorod 603950, Russia.
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