Alexander Bagaturyants received his Ph.D. in Physical Chemistry from the Institute of Organoelement Chemistry of USSR Academy of Sciences in 1968, and his Dr. Sci. in Physical Chemistry from the Institute of Chemical Physics of USSR Academy of Sciences in 1988. He joined Photochemistry Center of Russian Academy of Sciences from its foundation in 1998, and since then and currently he is head of laboratory of quantum chemistry and molecular simulations. Since 2009, he holds the position of a professor at the Department of Condensed Matter Physics of the National Research Nuclear University “MEPhI”. His main research interests deal with first-principles DFT calculations of molecular systems, excited states and esciplexes, organic nanophotonics, semiconductor surfaces, charge transport etc.
The photogeneration of charges in bulk heterojunction organic photovoltaics is of crucial importa... more The photogeneration of charges in bulk heterojunction organic photovoltaics is of crucial importance in the mechanism of charge separation. This results in the formation of both locally excited and charge-transfer exciplex states. While the former states are prone to radiative or nonradiative recombination, the latter ones can have a sufficiently long lifetime. In this work, the formation of charge-transfer exciplex states in pairs of PC61BM (acceptor) with different oligothiophenes (donors) is studied theoretically using density functional theory. The ground and excited states of three oligothiophene-PC61BM complexes are studied. It is found that the intensively absorbing state is localized on the oligothiophene. Another excited state is localized on PC61BM, being characterized by only slight absorption. The charge-transfer (CT) excited state of the complex lies either below or slightly higher than the locally excited (LE) states. The latter case is unfavorable for charge separation. Criteria for the efficient formation of charge-transfer exciplexes are found, and the possibility of oligothiophene modification to facilitate the formation of such exciplexes is explored. Shifting the donor absorption to the near IR, which is important for organic solar cells, is another goal of oligothiophene modification. A modified oligothiophene satisfying these two criteria is proposed. The structure and radiative lifetimes of the LE and CT states and also the binding energy of the CT states with respect to their dissociation into a radical cation and a radical anion are calculated. It is demonstrated that the lifetime of the CT exciplexes is sufficiently long to accomplish charge separation.
The extremely high scintillation efficiency of lutetium iodide doped by cerium is explained as a ... more The extremely high scintillation efficiency of lutetium iodide doped by cerium is explained as a result of several factors controlling the energy transfer from the host matrix to activator, two of which are investigated in the present paper. The first one is the increase of the efficiency of energy transfer from self-trapped excitons to cerium ions in the row LuCl3-LuBr3-LuI3. The STE structure and the efficiency of STE to cerium energy transfer are verified by cluster ab initio calculations. We propose and theoretically validate the possibility of a new channel of energy transfer to excitons and directly to cerium, namely the Auger process when Lu 4f hole relaxes to the valence band hole with simultaneous creation of additional exciton or excitation of cerium. This process should be efficient in LuI3, and inefficient in LuCl3. In order to justify this channel we perform calculations of density of states using a periodic plane-wave density functional approach. The performed estimati...
SrFeO3-δ is mixed ionic-electronic conductor with complex magnetic structure which reveals also c... more SrFeO3-δ is mixed ionic-electronic conductor with complex magnetic structure which reveals also colossal magnetoresistance effect. This material and its solid solutions are attractive for various spintronic, catalytic and electrochemical applications,...
Abstract. Recent progress in several related research areas such as first-principles electronic-s... more Abstract. Recent progress in several related research areas such as first-principles electronic-structure calculations of atoms and diatomic molecules, theory of elementary processes, kinetics, and numerical engineering, and also continued exponential growth in ...
BiFeO3 perovskite attracts great attention due to its multiferroic properties and potential use a... more BiFeO3 perovskite attracts great attention due to its multiferroic properties and potential use as a parent material for Bi1-xSrxFeO3-δ and Bi1-xSrxFe1-yCoyO3-δ solid solutions in intermediate temperature cathodes of oxide fuel cells. Another iron-based LaFeO3 perovskite is the end member for well-known solid solutions (La1-xSrxFe1-yCoyO3-δ) used for oxide fuel cells and other electrochemical devices. In this study an ab initio hybrid functional approach was used for the study of the thermodynamic stability of both LaFeO3 and BiFeO3 with respect to decompositions to binary oxides and to elements, as a function of temperature and oxygen pressure. The localized (LCAO) basis sets describing the crystalline electron wave functions were carefully re-optimized within the CRYSTAL09 computer code. The results obtained by considering Fe as an all-electron atom and within the effective core potential technique are compared in detail. Based on our calculations, the phase diagrams were construc...
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2017
A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one ... more A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one of the phenyl rings at the para-position were synthesized and used to elucidate the effects of changing the attached halogen atom on the photophysical properties of BF2DBM. The room-temperature absorption and fluorescence maxima of fluoro-, chloro-, bromo- and iodo-substituted derivatives of BF2DBM in THF are red-shifted by about 2-10nm relative to the corresponding peaks of the parent BF2DBM. The fluorescence quantum yields of the halogenated BF2DBMs (except the iodinated derivative) are larger than that of the unsubstituted BF2DBM. All the synthesized compounds are able to form fluorescent exciplexes with benzene and toluene (emission maxima at λem=433 and 445nm, respectively). The conformational structure and electronic spectral properties of halogenated BF2DBMs have been modeled by DFT/TDDFT calculations at the PBE0/SVP level of theory. The structure and fluorescence spectra of exciplexes were calculated using the CIS method with empirical dispersion correction.
The photogeneration of charges in bulk heterojunction organic photovoltaics is of crucial importa... more The photogeneration of charges in bulk heterojunction organic photovoltaics is of crucial importance in the mechanism of charge separation. This results in the formation of both locally excited and charge-transfer exciplex states. While the former states are prone to radiative or nonradiative recombination, the latter ones can have a sufficiently long lifetime. In this work, the formation of charge-transfer exciplex states in pairs of PC61BM (acceptor) with different oligothiophenes (donors) is studied theoretically using density functional theory. The ground and excited states of three oligothiophene-PC61BM complexes are studied. It is found that the intensively absorbing state is localized on the oligothiophene. Another excited state is localized on PC61BM, being characterized by only slight absorption. The charge-transfer (CT) excited state of the complex lies either below or slightly higher than the locally excited (LE) states. The latter case is unfavorable for charge separation. Criteria for the efficient formation of charge-transfer exciplexes are found, and the possibility of oligothiophene modification to facilitate the formation of such exciplexes is explored. Shifting the donor absorption to the near IR, which is important for organic solar cells, is another goal of oligothiophene modification. A modified oligothiophene satisfying these two criteria is proposed. The structure and radiative lifetimes of the LE and CT states and also the binding energy of the CT states with respect to their dissociation into a radical cation and a radical anion are calculated. It is demonstrated that the lifetime of the CT exciplexes is sufficiently long to accomplish charge separation.
The extremely high scintillation efficiency of lutetium iodide doped by cerium is explained as a ... more The extremely high scintillation efficiency of lutetium iodide doped by cerium is explained as a result of several factors controlling the energy transfer from the host matrix to activator, two of which are investigated in the present paper. The first one is the increase of the efficiency of energy transfer from self-trapped excitons to cerium ions in the row LuCl3-LuBr3-LuI3. The STE structure and the efficiency of STE to cerium energy transfer are verified by cluster ab initio calculations. We propose and theoretically validate the possibility of a new channel of energy transfer to excitons and directly to cerium, namely the Auger process when Lu 4f hole relaxes to the valence band hole with simultaneous creation of additional exciton or excitation of cerium. This process should be efficient in LuI3, and inefficient in LuCl3. In order to justify this channel we perform calculations of density of states using a periodic plane-wave density functional approach. The performed estimati...
SrFeO3-δ is mixed ionic-electronic conductor with complex magnetic structure which reveals also c... more SrFeO3-δ is mixed ionic-electronic conductor with complex magnetic structure which reveals also colossal magnetoresistance effect. This material and its solid solutions are attractive for various spintronic, catalytic and electrochemical applications,...
Abstract. Recent progress in several related research areas such as first-principles electronic-s... more Abstract. Recent progress in several related research areas such as first-principles electronic-structure calculations of atoms and diatomic molecules, theory of elementary processes, kinetics, and numerical engineering, and also continued exponential growth in ...
BiFeO3 perovskite attracts great attention due to its multiferroic properties and potential use a... more BiFeO3 perovskite attracts great attention due to its multiferroic properties and potential use as a parent material for Bi1-xSrxFeO3-δ and Bi1-xSrxFe1-yCoyO3-δ solid solutions in intermediate temperature cathodes of oxide fuel cells. Another iron-based LaFeO3 perovskite is the end member for well-known solid solutions (La1-xSrxFe1-yCoyO3-δ) used for oxide fuel cells and other electrochemical devices. In this study an ab initio hybrid functional approach was used for the study of the thermodynamic stability of both LaFeO3 and BiFeO3 with respect to decompositions to binary oxides and to elements, as a function of temperature and oxygen pressure. The localized (LCAO) basis sets describing the crystalline electron wave functions were carefully re-optimized within the CRYSTAL09 computer code. The results obtained by considering Fe as an all-electron atom and within the effective core potential technique are compared in detail. Based on our calculations, the phase diagrams were construc...
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2017
A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one ... more A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one of the phenyl rings at the para-position were synthesized and used to elucidate the effects of changing the attached halogen atom on the photophysical properties of BF2DBM. The room-temperature absorption and fluorescence maxima of fluoro-, chloro-, bromo- and iodo-substituted derivatives of BF2DBM in THF are red-shifted by about 2-10nm relative to the corresponding peaks of the parent BF2DBM. The fluorescence quantum yields of the halogenated BF2DBMs (except the iodinated derivative) are larger than that of the unsubstituted BF2DBM. All the synthesized compounds are able to form fluorescent exciplexes with benzene and toluene (emission maxima at λem=433 and 445nm, respectively). The conformational structure and electronic spectral properties of halogenated BF2DBMs have been modeled by DFT/TDDFT calculations at the PBE0/SVP level of theory. The structure and fluorescence spectra of exciplexes were calculated using the CIS method with empirical dispersion correction.
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