Bozhenko Konstantin Viktorovich
1971

Se graduó en la Universidad Estatal de Voronezh, el Departamento de Física Teórica, la tesis de grado se realizó en química cuántica en el INKhP (el Instituto de Nuevos Problemas Químicos) de la Academia de Ciencias de la URSS.

1979

Defendió su Tesis de Candidato a Doctor sobre el tema de “El estudio teórico de los estados de valencia de los átomos en las moléculas inorgánicas mediante el método de Hartree – Fock – Rutan”.

1990 ‒ 1996

Investigador Científico, Investigador Científico Principal del Instituto de Física Química “N.N. Semenov” de la Academia de Ciencias de Rusia. 

1996 ‒ 2004

Investigador Científico Principal del Instituto de Física Bioquímica “N.M. Emanuel” de la Academia de Ciencias de Rusia.

2000

Defendió su tesis doctoral sobre el tema de “Los modelos cuánticos-químicos en el estudio de la estructura electrónica y la reactividad de las pequeñas moléculas insaturadas de valencia de elementos no transicionales”.

De 2004 hasta el presente

Investigador Científico Principal del Instituto de Física Bioquímica de la Academia de Ciencias de Rusia.

De 2001 hasta el presente

Profesor Titular del Departamento de Química Física y Coloide de la RUDN.

2005
  • Fue galardonado con el título de Catedrático de la Universidad en el Departamento de Química Física y Coloide de la RUDN. 
  • Fue galardonado con un diploma de la Presidencia de la Academia de Ciencias de Rusia. 
  • Miembro del Consejo de Redacción de la Revista de “Comunicaciones de Butlerov”.

Docencia

  • Imparte el curso general de “Los fundamentos de la química cuántica”, las conferencias sobre la química cuántica y los cursos especiales sobre “Los problemas actuales de la química moderna” y “Los capítulos seleccionados de la química cuántica”.
  • Con la participación de Konstantin Bozhenko, comenzó la cooperación internacional activa del Departamento de Química Física y Coloide de la RUDN con el Departamento de Química y Bioquímica de la Universidad Estadounidense del Estado de Utah (UEU) en la defensa de las tesis de doctorado.  

Ciencia

  • Fue propuesto un modelo para predecir las proporciones de la energía de activación en las reacciones de introducción en el enlace con la participación de las moléculas insaturadas de valencia sobre la base de los espectros de agentes químicos aislados. Fue mostrada la posibilidad de ordenamiento ferromagnético en una fase de carbono particular, intermedia entre el grafito y el diamante. Por primera vez, se realizó la modelación química cuántica de polinitrenos de alto espín y se desarrollaron los enfoques para el análisis de los parámetros magnéticos de estos sistemas. Se mostró la posibilidad de la existencia de dobles espirales en los compuestos inorgánicos. Se investigaron las características de la aromaticidad del grafeno. Se descubrieron las estructuras inusuales de los compuestos de boro - carbono, cuya existencia fue comprobada mediante experimentos.
  • Los más conocidos son los estudios del Catedrático de la Universidad sobre el desarrollo de la teoría de ferromagnetos orgánicos (en cooperación con el miembro correspondiente de la Academia de Ciencias de Rusia, A.A. Ovchinnikov), la extinción del dioxígeno singlete (en cooperación con el equipo del académico I.I. Moiseev), el diseño computarizado de materiales bifuncionales (en cooperación con los académicos S. M. Aldoshin y V.I.  Minkin).
  • Es especialista en el campo de la química cuántica no empírica. Es autor de más de 220 trabajos científicos dedicados al estudio de ferromagnetos orgánicos, reacciones químicas elementales, el problema de la extinción del dioxígeno singlete en presencia de las partículas paramagnéticas, el estudio del smog fotoquímico en la atmósfera, así como el estudio de los óxidos de metales de transición y la modelación por ordenador de las interacciones de intercambio en la subred magnética de materiales bifuncionales.
  •  

Intereses Científicos

La química cuántica no empírica y la implementación sobre su base del diseño computarizado y la investigación de la estructura de compuestos químicos con parámetros dados para la creación de nuevos materiales, tales como los ferromagnetos orgánicos y los materiales bifuncionales con propiedades ferromagnéticas y fotocrómicas. El desarrollo de la teoría de reactividad de moléculas insaturadas de valencia. La reactividad de ferromagnetos orgánicos y las características de la estructura y propiedades de los óxidos de metales de transición.

G.L. Gutsev, K.G. Belay, K.V. Bozhenko, L.G. Gutsev and B.R. Ramachandrand. A comparative study of small 3d-metal oxide (FeO)n, (CoO)n, and (NiO)n clusters. Phys. Chem. Chem. Phys., (2016) 18, 27858 -27867. doi: 10.1039/c6cp03241a.
Geometrical and electronic structures of the 3d-metal oxide clusters (FeO)n, (CoO)n, and (NiO)n are computed using density functional theory with the generalized gradient approximation in the range of 1 r n r 10. It is found that the cluster geometries are similar in the (FeO)n and (CoO)n series but noticeably different in the (NiO)n series for several values of n. All of the lowest total energy states are found to possess relatively small spin multiplicities and are either antiferromagnetic or ferromagnetic except for the states of (NiO)3, (NiO)4, (NiO)9, and (NiO)10, which are ferromagnetic. The computed polarizabilities per atom undergo a steep decrease when compared to the atomic values of the MO monomers (M = Fe, Co, and Ni). Surprisingly, the polarizability does not strongly depend on either M or n in all the considered series when n varies from 3 to 10. The binding energies per atom are the largest in the (FeO)n series, followed by the binding energies of (CoO)n and (NiO)n.
G.L. Gutsev, K.V. Bozhenko, L. G. Gutsev, A.N. Utenyshev, and S.M. Aldoshin. Transitions from Stable to Metastable States in the Cr2On and Cr2On− Series, n =1−14. J. Phys. Chem. A (2017) 121, 845−854. doi: 10.1021/acs.jpca.6b11036.
The geometrical and electronic structures of the Cr2On and Cr2On− clusters are computed using density functional theory with a generalized gradient approximation in the range of 1 ≤ n ≤ 14. Local total spin magnetic moments, polarizabilities, binding energies per atom, and energies of abstraction of O and O2 are computed for both series along with electron affinities of the neutrals and verticaldetachment energies of the anions. In the lowest total energies states of Cr2O2,Cr2O3, Cr2O4,Cr2O14,Cr2O3−,Cr2O4−, and Cr2O14−, total spin magnetic moments of the Cr atoms are quite large and antiferromagnetically coupled. In the rest of the series, atleast one of the Cr atoms has no spin-magnetic moment at all. The computed vertical electron-detachment energies of the Cr2On− are in good agreement with experimental values obtained in the 1 ≤ n ≤ 7 range. All neutral Cr2On possess electron affinities larger than the electron affinities of halogen atoms when n > 6 and are thus superhalogens. It is found that the neutrals and anions are stable with respect to the abstraction of an O atom in the whole range of n considered, whereas both neutrals and anions became unstable toward the loss of O2 for n >7. The polarizability per atom decreases sharply when n moves from one to four and then remains nearly constant for larger n values in both series. The largest members in both series, Cr2O14 and Cr2O14−, possess the geometrical structures of the Cr2(O2)7 type by analogy with monochromium Cr(O2)4.
Sergey M. Aldoshin, Konstantin V. Bozhenko and Andrey N. Utenyshev. Quantum-chemical modeling of exchange coupling in the magnetic sublattice of bifunctional compounds containing heterometallic complexes of 3d and 4d metals with oxalate and dithiooxamide ligands. Structural Chemistry (2017) 28:965-974. doi: 10.1007/s11224-016-0900-0.
To find components of the magnetic sub-lattice of bi-functional compounds with maximum ferromagnetic exchange coupling, quantum-chemical calculations of complexes [(L)2M1III(L)M2II(L)2]5- are performed (M1III and M2II are tri- and divalent atoms of 3d and 4d transition metals M1III (Cr, Mo) and M2II (Ni, Co, Tc, Ru, Rh, Pd), L is dithiooxamide or oxalate). Calculations of the geometric structure of the complex are performed at the B3LYP/LANL2DZ level and calculations of J constants are performed at the B3LYP/TZV level. The replacement of a divalent atom of 3d metal by a divalent atom of 4d metal leads to an increase of J, whereas the replacement of a trivalent atom of 3d metal by a trivalent atom of 4d metal does not change the value of J. It is concluded that there is a correlation of J with a total change in the spin density on the M1III and M2II metals in the complexes compared to the M13+ and M22+ isolated cations.
Aldoshin S.M., Sanina N.A., Korchagin D.V., Shilov G.V., Mushenok F.B., Utenyshev A.N., Bozhenko K.V., Antipin I.S., Soloveva S.E. EXPERIMENTAL AND THEORETICAL STUDY OF THE INFLUENCE OF PERIPHERAL ENVIRONMENT ON MAGNETIC PROPERTIES OF TETRANUCLEAR MANGANESE SKELETON IN NEW REPRESENTATIVES OF CALIX[4]ARENE-CONTAINING [MNII2 MNIII2] CLUSTERS. Journal of Molecular Structure. (2015) V.1081 pp. 217-223. ISSN: 0022-2860, DOI: 10.1016/j.molstruc.2014.10.022.
Получен новый представитель каликс[4]аренсодержащих тетраядерных марганцевых комплексов типа [MNII2MNIII2] с 2,2'-дипиридилбидентатным лигандом, координированным в экваториальной плоскости комплекса (II). Комплекс кристаллизуется в моноклинной космической группе P21 / c (a = 14,9402 (7) Å, b = 32,816 (1) Å, c = 21,595 (1) Å, β = 106,888 (4)). Его магнитные свойства изучались методом СКВИД-магнитометрии. Показано, что замещение периферического лиганда существенно влияет на структуру центрального фрагмента металлического комплекса и, следовательно, на магнитные свойства. Для этого комплекса и для аналогичного каликс[4]аренсодержащего марганцевого комплекса с пиридиновым лигандом (I) были выполнены квантово-химические расчеты. Было выяснено влияние периферийной среды на магнитные свойства тетраядерного марганцевого скелета для обоих комплексов
Kovalchukova O.V., Aldoshin S.M., Utenyshev A.N., Bozhenko K.V. , Valeriy Tkachev. SYNTHESIS, CRYSTAL AND MOLECULAR STRUCTURE OF CATENA-(BIS(μ1- OXALIC ACID)-μ3-HYDROGEN OXALATE-DI-AQUA-SODIUM(I)) Communications in Inorganic Synthesis. 2015, Vol.3, № 2, 23-25.
Кристаллическая и молекулярная структура катена-(бис(μ-щавелевой кислоты)-μ-оксалата-ди-аква-натрия (I)) была обнаружена рентгеновским анализом. Соединение кристаллизуется в триклинной пространственной группе P-1 с (Å) 6,2378 (12); B (Å) 71115 (14); C (Å) 10,489 (2); Α (°) 94,65 (3); Β (°) 100,12 (3); Γ (°) 97,78 (3). Катион натрия в названном соединении составляет восемь координированных и образует квадратный антипринт. Он окружен двумя молекулами щавелевой кислоты, одним водорастворимым анионом и одной молекулой воды. Как щавелевая кислота, так и водородный оксалат-анион действуют совместно как полидентатные мостиковые лиганды. Центросимметричные катионы натрия ограничены анионами оксалата водорода через систему связей H, связанных с молекулами щавелевой кислоты. В решетке формируется трехмерная структура, стабилизированная водородными связями.
Emel'yanova N., Sanina N., Krivenko A., Manzhos R., Bozhenko K., Aldoshin S. COMPARISON OF PURE AND HYBRID DFT FUNCTIONALS FOR GEOMETRY OPTIMIZATION AND CALCULATION OF REDOX POTENTIALS FOR IRON NITROSYL COMPLEXES WITH "L-SCN" BRIDGING LIGANDS. Theoretical Chemistry Accounts: Theory, Computation, and Modeling. Theor. Chem. Acc. (2013) 132:1316.
The geometry and electronic structure of neutral molecules and mono-anions of iron nitrosyl complexes with “μ-SCN” bridging ligands [(μ-SC7H4SN)Fe(NO)2]2 (I) and [(μ-SC2H3N4)Fe(NO)2]2 (II) were studied using the density functional theory: pure functionals BP86, OLYP, OPBE, TPSS, PW91 and hybrid functionals B3LYP, B1B95, B3PW91 along with 6-311++G**//6-31G*. For geometry optimization, the pure functionals are more appropriate than the hybrid functionals. For mono-anions, pure functionals favor the doublet over the quartet state by 8.0–13.9 kcal/mol, whereas hybrid functionals yield quartet spin state of these anions to be more stable. The redox potentials of complexes I and II have been computed by DFT and compared with experimental results obtained from cyclic voltammetry method. The calculated redox potentials for I and II with pure functionals (especially BP86) are close to the experimental values, whereas those obtained by using hybrid functionals significantly deviate from the experiment.
We report a theoretical investigation on the ten-atom boron-carbon mixed clusters CxB10 − x− (x = 3-10), revealing a molecular wheel to monocyclic ring and linear species structural change as a function of x upon increasing the number of carbon atoms in the studied series. The unbiased searches for the global minimum structures of the clusters with x ranging from 3 to 9 were conducted using the Coalescence Kick program for different spin multiplicities. Subsequent geometry optimizations with follow-up frequency calculations at the hybrid density functional B3LYP/6-311+G(d) level of theory along with the single point coupled-cluster calculations (UCCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(d) and RCCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(d)) revealed that the C3B7− and C4B6− clusters possess planar distorted wheel-type structures with a single inner boron atom, similar to the recently reported CB9− and C2B8−. Going from C5B5− to C9B− inclusive, monocyclic and ring-like structures are observed as the most stable ones on the PES. The first linear species in the presented series is found for the C10− cluster, which is almost isoenergetic with the one possessing a monocyclic geometry. The classical 2c-2e σ bonds are responsible for the peripheral bonding in both carbon- and boron-rich clusters, whereas multicenter σ bonding (nc-2e bonds with n > 2) on the inner fragments in boron-rich clusters is found to be the effective tool to describe their chemical bonding nature. It was shown that the structural transitions in the CxB10-x− series occur in part due to the preference of carbon to form localized bonds, which are found on the periphery of the clusters. Chemical bonding picture of C10− is explained on the basis of the geometrical structures of the C10 and C102− clusters and their chemical bonding analyses.
Ivanov A.S., Boldyrev A.I., Morris A.J., Pickard C.J., Bozhenko K.V. INORGANIC DOUBLE-HELIX STRUCTURES OF UNUSUALLY SIMPLE LITHIUM-PHOSPHORUS SPECIES Angewandte Chemie - International Edition. (2012) 51 8330. DOI: 10.1002/anie.201201843
Выполнены прецизионные квантово-химические расчеты некоторых структур фосфида лития и показана возможность существования двойных спиральных структур в классе неорганических соединений.
Ivanov A.S., Bozhenko K.V., Boldyrev A.I. ON THE SUPPRESSION MECHANISM OF THE PSEUDO-JAHN-TELLER EFFECT IN MIDDLE E6 (E = P, AS, SB) RINGS OF TRIPLE-DECKER SANDWICH COMPLEXES Inorganic Chemistry. (2012) 51 8868.
Quantum chemical calculations of the CpMoE6MoCp (E = P, As, Sb) triple-decker sandwich complexes showed that E6 fragments in the central decks of the complexes are planar. Analysis of molecular orbitals involved in vibrational coupling demonstrated that filling the unoccupied molecular orbitals involved in vibronic coupling with electron pairs of Mo atoms suppresses the PJT effect in the CpMoE6MoCp (E = P, As, Sb) sandwich, with the E6 ring becoming planar (D6h) upon complex formation. The AdNDP analysis revealed that bonding between C5H5− units and Mo atoms has a significant ionic contribution, while bonding between Mo atoms and E6 fragment becomes appreciably covalent through the δ-type M → L back-donation mechanism.
Ivanov A.S., Bozhenko K.V., Boldyrev A.I. PECULIAR TRANSFORMATIONS IN THE CXHXP4-X (X = 0-4) SERIES Journal of Chemical Theory and Computation. (2012) 8, 135–140. dx.doi.org/10.1021/ct200727z .
ABSTRACT: In the current work, we performed a systematic study of the CxHxP4Аx (x =0А4) series using an unbiased CK global minimum and low-lying isomers search for the singlet and triplet P4АC4H4 species at the B3LYP/6-31G** level of theory. The selected lowest isomers were recalculated at the CCSD(T)/CBS//B3LYP/6-311++G** level of theory. We found that the transition from a three-dimensional tetrahedron-like structure to a planar structure occurs at x = 3, where planar isomers become much more stable than the tetrahedral structures due to significantly stronger π bonds between carbon atoms in addition to increasing strain energy at the carbon atom in the tetrahedral environment.
Popov I.A., Boldyrev A.I., Bozhenko K.V. IS GRAPHENE AROMATIC? Nano Research. 2012 5(2) 117-123.
Using adaptive natural density partitioning analysis we prove that graphene is aromatic, but its aromaticity is different from the aromaticity in benzene, coronene, or circumcoronene. Aromaticity in graphene is local with two π-electrons delocalized over every hexagon ring.
In this joint experimental and theoretical work we present a novel type of structural transition occurring in the series of CxB8-x─ (x = 1–8) mixed clusters upon increase of the carbon content from x =2 to x = 3. The wheel to ring transition is surprising because it is rather planar-to-linear type of transition to be expected in the series since B8,B8А,B82А and CB7А are known to possess wheel-type global minimum structures while C8 is linear.
Misochko E.Y., Korchagin D.V., Bozhenko K.V., Chapyshev S.V., Aldoshin S.M. A DENSITY FUNCTIONAL THEORY STUDY OF THE ZERO-FIELD SPLITTING IN HIGH-SPIN NITRENES Journal of Chemical Physics. (2010) v. 133, p. 4101-4110.
This work presents a detailed evaluation of the performance of density functional theory (DFT) for the prediction of zero-field splittings (ZFSs) in high-spin nitrenes. A number of well experimentally characterized triplet mononitrenes, quartet nitrenoradicals, quintet dinitrenes, and septet trinitrenes have been considered. Several DFT-based approaches for the prediction of ZFSs have been compared. It is shown that the unrestricted Kohn-Sham and the Pederson-Khanna approaches are the most successful for the estimation of the direct spin-spin (SS) interaction and the spin-orbit coupling (SOC) parts, respectively, to the final ZFS parameters. The most accurate theoretical predictions (within 10%) are achieved by using the PBE density functional in combination with the DZ, EPR-II, and TZV basis sets. For high-spin nitrenes constituted from light atoms, the contribution of the SOC part to ZFS parameters is quite small (7%-12%). By contrast, for chlorine-substituted septet trinitrenes, the contribution of the SOC part is small only to D value but, in the case of E value, it is as large as the SS part and has opposite sign. Due to this partial cancellation of two different contributions, SS and SOC, the resulting values of E in heavy molecules are almost two times smaller than those predicted by analysis of the widely used semiempirical one-center spin-spin interaction model. The decomposition of D(SS) into n-center (n=1-4) interactions shows that the major contribution to D(SS) results from the one-center spin-spin interactions. This fact indicates that the semiempirical SS interaction model accurately predicts the ZFS parameters for all types of high-spin nitrenes with total spin S=2 and 3, if their molecules are constructed from the first-row atoms.
Timokhina H.N., Ovchinnikov A.A., Bozhenko K.V. AB INITIO QUANTUM CHEMICAL CALCULATIONS OF A CLUSTER C8H12 International Journal of Quantum Chemistry. (2002) 88(4) 433–435.
Using unrestricted Hartree–Fock–Roothaan approximation and density functional theory on 6-31G* basis, ab initio calculation cluster C8H12 has been carried out. It was shown asa result of calculations thata ground state for the conformation given isa septet state. This cluster can be used for investigation of the kinematic mechanism of magnetic exchange and magnetic ordering in polyradicals.
Bozhenko K.V., Ovchinnikov A.A. NON-EMPIRICAL MOLECULAR ORBITAL STUDIES OF THE POSSIBILITY OF FERROMAGNETIC ORDERING IN ISOELECTRON-SUBSTITUTED FERROCARBON MODIFICATIONS Computational and Theoretical Chemistry. (1995) 343, 177-182.
The vertical singlet-triplet (ST) splitting in the C3H6 molecule and C2BH-6 and C2NH+6 ions has been investigated by means of ab initio calculations. The molecular geometry was either taken as that corresponding to the UHF/6-31G* or UHF/6-31+G* energy minimum of the triplet configuration (for C3H6, C2BH-6, C2NH+6), or was extracted from the ferrocarbon crystal (for C3H6). Polarized split-valence basis sets (6-31G*, 6-31+G* and 6-311G**) and fourth-order Moller-Plesset perturbation theory at the MP4SDTQ level of approximation provides more reliable ST splitting values, than the MP4SDQ level, the latter being the most accurate method used in our previous work. These calculations prove the presence of ferromagnetic ordering within the same quasi-graphite plane of ferrocarbon crystal. The presence of such ordering has been shown within the same quasi-graphite plane upon substitution of sp3 carbon atoms by ions B-, N+ and so on.