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  • 1. Fromager, E.
    et al.
    Vallet, V.
    Schimmelpfennig, B.
    Macak, P.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Wahlgren, U.
    Spin-orbit effects in electron transfer in neptunyl(VI)-neptunyl(V) complexes in solution2005In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 109, no 22, p. 4957-4960Article in journal (Refereed)
    Abstract [en]

    The spin-orbit effects were investigated on the complexes involved in the electron self-exchange between Np(V) and Np(VI) in both the outer-sphere and inner-sphere mechanisms, the latter for binuclear complexes containing hydroxide, fluoride, and carbonate as bridging ligands. Results obtained with the variation-perturbation and the multireference single excitation spin-orbit Cl calculations are compared. Both effects due to different relaxations of spinors within a multiplet (spin-orbit relaxation) and scalar (electrostatic) relaxation effects in the excited states are accounted for in the latter scheme. The results show that the scalar (electrostatic) relaxation is well described by the single-excitation spin-orbit CI, and that spin-orbit relaxation effects are small in the Np complexes, as in the lighter d-transition elements but in contrast to the main group elements.

  • 2.
    Frölander, Anders
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Lutsenko, Serghey
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Conformational preferences and enantiodiscrimination of phosphino-4-(1-hydroxyalkyl)oxazoline-metal-olefin complexes resulting from an OH-metal hydrogen bond2005In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 70, no 24, p. 9882-9891Article in journal (Refereed)
    Abstract [en]

    Phosphinooxazolines carrying (1-hydroxy-1-phenyl)methyl and (1-methoxy-1-phenyl)methyl substituents in the 4 position of the oxazoline ring exhibit contrasting behavior in Pd-and Ir-catalyzed allylic alkylations. Whereas catalysts with the methoxy-containing ligand generally provide products with high ee's, use of catalysts prepared from the hydroxy-containing ligand results in products with low ee's or even racemates. DFT calculations suggest the presence of a hydrogen bond with Pd(0) as the proton acceptor in the hydroxy-containing olefin-Pd(0) complexes, which induces a conformational change in the ligand, leading to different stereoselectivity.

  • 3.
    Frölander, Anders
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Lutsenko, Serghey
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    OH-Metal hydrogen bond in Pd- and Ir-catalyzed allylic alkylations2006In: ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2006, p. ORGN-259-Conference paper (Other academic)
    Abstract [en]

    Phosphinooxazolines carrying 4-hydroxybenzyl and 4-methoxybenzyl substituents exhibit contrasting behavior in Pd- and Ir-catalyzed allylic alkylations.  Whereas catalysts with the methoxy-contg. ligand generally provide products with high ee's, use of catalysts prepd. from the hydroxy contg. ligand results in products with low ee's or even racemates.  DFT calcns. suggest the presence of a hydrogen bond with Pd(0) as proton acceptor in the hydroxy contg. olefin Pd(0) complexes, which induces a conformational change in the ligand leading to different stereoselectivity.  We have previously obsd. the same kind of dramatic changes of enantioselectivities in palladium-catalyzed allylations upon methylation of hydroxy-contg. pyridinooxazolines and bisoxazolines.

  • 4. Gelmukhanov, F
    et al.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    Ågren, Hans
    KTH, Superseded Departments, Chemistry.
    Collapse of vibrational structure in spectra of resonant x-ray Raman scattering1997In: Physical Review A. Atomic, Molecular, and Optical Physics, ISSN 1050-2947, E-ISSN 1094-1622, Vol. 56, no 1, p. 256-264Article in journal (Refereed)
    Abstract [en]

    Extreme narrowing, or collapse, of electron-vibrational bands is predicted as a new phenomenon in resonant radiative and nonradiative x-ray scattering (RXS) spectra. It is shown that in the inelastic scattering case, that is, when the potential surfaces of ground and final slates are different, a considerable narrowing of the vibronic RXS band results from detuning the excitation Photon frequency omega away from the absorption resonance. By fine tuning the frequency, this may under special circumstances also occur in the region of strong photoabsorption. In the case of elastic Rayleigh scattering, that is, when the potential surfaces of ground and final states are identical, the narrowing results in a total collapse to a single resonance by detuning the frequency. The theory predicts how the differencies in vibrational structure of resonant and nonresonant photoemission spectra depends on the excitation frequency. The effect of frequency detuning on complex spectral multilevel structures due to multiplet: and spin-orbit splittings is discussed qualitatively. It is shown that the notion of: duration time for the x-ray scattering process plays a crucial role in the understanding of RXS spectra.

  • 5. Gelmukhanov, F
    et al.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    Ågren, Hans
    KTH, Superseded Departments, Chemistry.
    Restoration of selection rules in nonadiabatic resonant inelastic x-ray scattering1997In: Journal of Experimental and Theoretical Physics, ISSN 1063-7761, E-ISSN 1090-6509, Vol. 85, no 1, p. 20-26Article in journal (Refereed)
    Abstract [en]

    Recently a new effect in the Raman scattering of x-ray radiation has been predicted theoretically and discovered in experiments, the effect of restoration of the selection rules for the scattering tensor under strong electron-vibrational interaction. We propose a fairly simple model for describing this effect, a model that allows for an exact solution and takes into account the real vibrational structure of the molecule and electron-vibrational interaction.

  • 6. Gel'mukhanov, F
    et al.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    Ågren, Hans
    KTH, Superseded Departments, Chemistry.
    Soft and hard x-ray Raman scattering by oriented symmetrical molecules: Selection rules, interference, and dephasing mechanisms1998In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 109, no 12, p. 5060-5069Article in journal (Refereed)
    Abstract [en]

    Resonant x-ray Raman scattering in chaotical, partial, and fixed oriented symmetric molecules is analyzed for x-ray photon excitation frequencies in both the soft and the hard x-ray regions. Different dephasing mechanisms and their connection with channel interference and the observation of selection rules are investigated. It is predicted that for harder x-ray energies the scattering cross sections become strongly anisotropic and oscillatory due to channel interference. The orientational dephasing is predicted to be an important coherence-blocking mechanism and can be introduced even by zero-point vibrational or librational motions. The connections between selection rules, symmetry and phase factors of the photon wave function, Bragg conditions and the channel interference show that the selection rules may operate for oriented, surface adsorbed, molecules even in the hard x-ray region. The possibility of using the interference effect for structure determination of adsorbates is discussed.

  • 7.
    Gel'mukhanov, Faris
    et al.
    KTH, Superseded Departments, Biotechnology.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    Temperature dependence and Debye-Waller factors for resonant x-ray Raman scattering in solids2000In: Physical Review B Condensed Matter, ISSN 0163-1829, E-ISSN 1095-3795, Vol. 62, no 21, p. 13996-14005Article in journal (Refereed)
    Abstract [en]

    Resonant x-ray Raman scattering is a strongly coherent process. The well defined phase relations between scattering channels through the core excited states localized at different atoms result in a conservation of the electronic crystal momentum. However, as we show here, the zero-point and thermal vibrations dephase these scattering channels and lead to incoherent contributions with different spectral shapes. The relative strength of the coherent and incoherent contributions are found to strongly depend on temperature via a Debye-Waller factor. This results in a characteristic temperature dependence of the spectral profile of the resonant x-ray Raman scattering.

  • 8.
    Gel’mukhanov, Faris
    et al.
    KTH, Superseded Departments, Biotechnology.
    Sałek, Paweł
    KTH, Superseded Departments, Biotechnology.
    Privalov, Timofei
    KTH, Superseded Departments, Biotechnology.
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    Duration of x-ray Raman scattering1999In: Physical Review A. Atomic, Molecular, and Optical Physics, ISSN 1050-2947, E-ISSN 1094-1622, Vol. 59, no 1, p. 380-389Article in journal (Refereed)
    Abstract [en]

    There has recently been much interest in using the notion of a duration time to analyze resonant x-ray Raman scattering (RXS) of atoms, molecules, and solids. This notion implies a selection of processes with different time scales responsible for the formation x-ray Raman spectra, and has been useful for actual predictions of various phenomena associated with RXS and that subsequently have been experimentally verified. However, the notion of a duration time for the x-ray scattering event can also have some paradoxical consequences, as when comparing the RXS duration with the relaxation time of the wave packet evolution in the case when the inverse detuning of the excitation energy is shorter than the time of flight or the lifetime of the core excited state. We present here a solution of this contradiction and give a detailed analysis of the notion of the duration time for RXS. It is shown that this time is complex and consists of two qualitatively different contributions. The first originates in the irreversible decay of the core excited state, while the imaginary part is caused by a reversible dephasing in the time domain. We investigate also the evolution of the wave packets of bound and dissociative states to stationary distributions. The theoretical analysis is accompanied by numerical examples of the time evolution of the wave packet in bound and dissociative core excited states of the N2 and HCl molecules.

  • 9. Macak, P.
    et al.
    Fromager, E.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Schimmelpfennig, B.
    Grenthe, I.
    Wahlgren, U.
    Electron transfer in neptunyl(VI)-neptunyl(V) complexes in solution2005In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 109, no 22, p. 4950-4956Article in journal (Refereed)
    Abstract [en]

    The rates and mechanisms of the electron self-exchange between Np(V) and Np(VI) in solution have been studied with quantum chemical methods and compared with previous results for the U(V)-U(VI) pair. Both outer-sphere and inner-sphere mechanisms have been investigated, the former for the aqua ions, the latter for binuclear complexes containing hydroxide, fluoride, and carbonate as bridging ligand. Solvent effects were calculated using the Marcus equation for the outer-sphere reactions and using a nonequilibrium PCM method for the inner-sphere reactions. The nonequilibrium PCM appeared to overestimate the solvent effect for the outer-sphere reactions. The calculated rate constant for the self-exchange reaction NpO2+(aq)+NpO22+(aq) &REVARR; NPO22+(aq)+NPO2+(aq), at 25° C is k = 67 M-1 s(-1), in fair agreement with the observed rates 0.0063-15 M-1 s-1. The differences between the Np(V)-Np(VI) and the U(V)-U(VI) pairs are minor.

  • 10. Nyhlén, Jonas
    et al.
    Duan, Lele
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Åkermark, Björn
    Sun, Licheng
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Privalov, Timofei
    Evolution of O-2 in a Seven-Coordinate Ru-IV Dimer Complex with a [HOHOH] (-) Bridge: A Computational Study2010In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 49, no 10, p. 1773-1777Article in journal (Refereed)
  • 11.
    Paavola, Sari
    et al.
    KTH, Superseded Departments, Chemistry.
    Zetterberg, Krister
    KTH, Superseded Departments, Chemistry.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    Csoregh, I.
    Moberg, Christina
    KTH, Superseded Departments, Chemistry.
    Aerobic oxidation of 1-phenylethanol catalyzed by palladaheterocycles2004In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 346, no 2-3, p. 237-244Article in journal (Refereed)
    Abstract [en]

    Cyclometallated palladium compounds with pyridine were shown to serve as more efficient catalysts for the aerobic oxidation of 1-phenylethanol than a previously investigated analogue with an oxazoline ring. Substituents with different electronic properties in the phenyl ring were shown to exhibit an only minor influence on the reactivity of the catalytic system. The first step in the reaction consists of the splitting of the acetate bridge in the dimeric starting complex and coordination of a ligand to palladium. By ab initio calculations it was shown that, in the presence of solvent, a complex with pyridine was more stable than that with the alcohol, whereas the opposite situation was found in the gas phase. The complex with coordinated alcohol was stabilized by hydrogen bonding. Good agreement was found between the computed structure and the X-ray structure of the initial palladaheterocycle 1.

  • 12. Plashkevych, O
    et al.
    Privalov, Timofei
    KTH, Superseded Departments, Biotechnology.
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    Carravetta, V
    Ruud, K
    On the validity of the equivalent cores approximation for computing X-ray photoemission and photoabsorption spectral bands2000In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 260, no 1-2, p. 11-28Article in journal (Refereed)
    Abstract [en]

    We evaluate the performance of the equivalent cores (Z + 1) approximation for computing core photoemission and photoabsorption spectral bands versus full self-consistent field optimizations. Franck-Condon factors are obtained using the linear coupling model with the multi-dimensional vibronic coupling constants computed from analytical calculations of the ground state frequencies and normal coordinates, and excited state energy gradients evaluated at the ground state equilibrium geometry. We use carbon monoxide, formaldehyde, chloromethanes and some monosubstituted benzenes for the purpose. Considering other inherent approximations in the calculations, we find that the equivalent core model works well for band shapes and comparatively better for excitations of strong modes and ionization of deeper core levels. The approximation also works somewhat better for photoemission than for discrete photoexcitation.

  • 13.
    Privalov, Timofei
    KTH, Superseded Departments, Biotechnology.
    Electronic and nuclear dynamics of X-ray processes2001Doctoral thesis, comprehensive summary (Other scientific)
  • 14.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    X-ray scattering by molecules, surface-adsorbates and solids with a coupling to the nuclear motion2000Licentiate thesis, comprehensive summary (Other scientific)
  • 15.
    Privalov, Timofei
    et al.
    KTH, Superseded Departments, Biotechnology.
    Gel’mukhanov, Faris
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    Role of electron-phonon interaction in resonant x-ray Raman scattering by polymers and solids1999In: Physical Review B. Condensed Matter and Materials Physics, ISSN 1098-0121, E-ISSN 1550-235X, Vol. 59, no 14, p. 9243-9258Article in journal (Refereed)
    Abstract [en]

    We present a theory of radiative resonant x-ray Raman scattering by solids and polymers beyond the Born-Oppenheimer approximation. The role of electron-phonon coupling of the intermediate core excited and final electronic states is analyzed in detail for π-electron systems and solids assuming the frozen-orbital approximation. The momentum exchange processes between valence electrons and phonons and with x-ray photons are analyzed, showing the similarities and differences between the two processes. The resonant inelastic x-ray scattering by a π-electron system is quenched up to zero in the Born-Oppenheimer approximation with frozen orbitals if the momentum exchange between valence electrons and x-ray photons is neglected. The electron-phonon and electron-photon interactions open the scattering channels for all occupied states in π systems. The frequency dependence of these effects is analyzed, showing that when the duration of the scattering is shortened by a large detuning of the excitation frequency, the role of electron-phonon coupling of both core-excited and final states is suppressed, depleting the cross section for π systems up to zero. The detuning quenches the symmetry breaking of the core-excited electronic states and results in a restoration of the selection rules and a conservation of electron momentum. Specific selection rules for the zero-phonon line in x-ray Raman spectra of linear polyenes are found. A detailed investigation of the narrowing, or collapse, of the electron-vibrational bands is given. When the detuning is large, the spectral profile is described by a joint density of states. It is predicted that the singularities of this joint density of states follows the Raman-Stokes dispersion law, something that allows a mapping of the band structure. We found that the phonon broadening of these singularities is completely quenched by detuning. A detailed investigation of the spectral shape versus detuning of the so-called excitonic band is given.

  • 16.
    Privalov, Timofei
    et al.
    KTH, Superseded Departments, Biotechnology.
    Gel'mukhanov, Faris
    KTH, Superseded Departments, Biotechnology.
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    Role of relaxation and time-dependent formation of x-ray spectra2001In: Physical Review B. Condensed Matter and Materials Physics, ISSN 1098-0121, E-ISSN 1550-235X, Vol. 64, no 16Article in journal (Refereed)
    Abstract [en]

    A fundamental problem of x-ray spectroscopy is the role of relaxation of the electronic subsystem in the field of the transient core hole. The main intention of the present study is to explore the dynamics due to core-hole relaxation in the whole time domain, and to find out how it is manifested in finite molecular systems in comparison with solids. A technique is developed based on a reduction of the Nozieres-De Dominicis equation to a set of linear algebraic equations. The developed time-dependent formalism is applied to a numerical investigation of a one-dimensional tight-binding model. The formation of the x-ray profiles is explored on the real time scale, and the role of interaction with the core hole, band filling, and the final-state rule are investigated for systems of different size. The fort-nation of spectra of the infinite translational invariant system is studied by extensions of the finite systems. We found that the dynamics of finite systems, like molecules, differs qualitatively from solids: Contrary to the latter the time lapse of the Nozieres-De Dominicis domain for finite systems is squeezed between the inverse bandwidth and the revival time, which is proportional to the system size. For small molecules this means that there is no time for a "Mahan-Nozieres-De Dominicis singularity" to develop. Comparison with the strict solution of the Nozieres-De Dominicis equation shows that the adiabatic approximation describes x-ray absorption and emission considerably better than the fast approximation. This explains the suppression of the relaxation effects in x-ray emission of, e.g., gas phase and surface adsorbed molecules, but also that these effects are essential for the absorption case. There is still a quantitative distinction between the adiabatic approximation and the strict approach, which becomes more important for larger systems. Adopting the so-called finite state rule by von Barth and Grossman also for molecules, an almost complete numerical agreement between this rule and the strict x-ray-absorption and emission profiles for systems of different sizes is obtained. The simulations indicate that the final-state rule correction is important mainly near the absorption edge and at the top of the emission band.

  • 17.
    Privalov, Timofei
    et al.
    KTH, Superseded Departments, Chemistry.
    Gel'mukhanov, Faris
    KTH, Superseded Departments, Biotechnology.
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    X-Ray absorption and photoionization of laser excited molecules2003In: Journal of Electron Spectroscopy and Related Phenomena, ISSN 0368-2048, E-ISSN 1873-2526, Vol. 129, no 1, p. 43-54Article in journal (Refereed)
    Abstract [en]

    This study presents theory and simulations of X-ray absorption and X-ray photoionization spectra of optically excited molecules. The simulations are carried out within a two-step excitation model in which the laser radiation prepares an optically excited state which subsequently is core-electron excited by X-rays. The model makes use of a newly derived time-dependent theory based on the Nozieres-De Dominicis equations. It describes the valence electron relaxation of the optically excited state in the field of the core hole and the implication of this relaxation on the formation of the X-ray spectra. It is found that an optical excitation results in a significant general enhancement of two-electron transitions giving rise to shake-up and shake-down type spectral lines in the X-ray spectra. The excitonic character of the optically excited states is found to considerably influence the formation of the X-ray spectral profile, something that is strongly size- and site-dependent.

  • 18.
    Privalov, Timofei
    et al.
    KTH, Superseded Departments, Biotechnology.
    Gel'mukhanov, Faris
    KTH, Superseded Departments, Biotechnology.
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    X-ray Raman scattering from molecules and solids in the framework of the Mahan-Nozieres-De Dominicis model2001In: Physical Review B. Condensed Matter and Materials Physics, ISSN 1098-0121, E-ISSN 1550-235X, Vol. 64, no 16Article in journal (Refereed)
    Abstract [en]

    We have developed a formulation of resonant x-ray Raman scattering of molecules and solids based on the Mahan-Nozieres-De Dominicis model. A key step in the formulation is given by a reduction of the Keldysh-Dyson equations for the Green's function to a set of linear algebraic equations. This gave way for a tractable scheme that can be used to analyze the resonant x-ray scattering in the whole time domain. The formalism is used to investigate the role of core-hole relaxation, interference, band filling, detuning, and size of the scattering target. Numerical applications are per-formed with a one-dimensional tight-binding model.

  • 19.
    Privalov, Timofei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Linde, C.
    Zetterberg, K.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Theoretical studies of the mechanism of aerobic alcohol oxidation with palladium catalyst systems2005In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 24, no 5, p. 885-893Article in journal (Refereed)
    Abstract [en]

    Density functional theory (DFT) was applied to a comprehensive mechanistic study of the Pd(II)-catalyzed oxidation of alcohols by molecular oxygen. Both parts of the catalytic cycle, i.e., the oxidative dehydrogenation of the substrate and the regeneration of the catalyst by the co-oxidant, molecular oxygen, were studied. The catalytic cycle under consideration consists of intramolecular deprotonation, beta-hydride elimination, and migratory insertion steps, and it is relevant for a wide class of catalytic systems. In particular, a Pd(II) cyclometalated system was addressed and qualitatively compared with the Uemura system (Pd(OAc)(2)/pyridine) and with the Pd-carbene system. Geometries of the intermediate complexes and relative Gibbs free energies were identified along the proposed reaction path with the help of computational methods. The transition state for the beta-hydride elimination, which is the highest point on the energy profile of the catalytic cycle, was identified.

  • 20.
    Privalov, Timofei
    et al.
    KTH, Superseded Departments, Chemistry.
    Macak, Peter
    KTH, Superseded Departments, Physics.
    Schimmelpfennig, B.
    Fromager, E.
    Grenthe, I.
    Wahlgren, Ulf
    KTH, Superseded Departments, Physics.
    Electron transfer in uranyl(VI)-uranyl(V) complexes in solution2004In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 126, no 31, p. 9801-9808Article in journal (Refereed)
    Abstract [en]

    The rates and mechanisms of the electron self-exchange between U(V) and U(VI) in solution have been studied with quantum chemical methods. Both outer-sphere and inner-sphere mechanisms have been investigated; the former for the aqua ions, the latter for binuclear complexes containing hydroxide, fluoride, and carbonate as bridging ligand. The calculated rate constant for the self-exchange reaction UO2+(aq) + UO22+(aq)UO22+(aq) + UO2+(aq), at 25 degreesC, is k = 26 M-1 s(-1). The lower limit of the rate of electron transfer in the inner-sphere complexes is estimated to be in the range 2 x 10(4) to 4 x 10(6) M-1 s(-1), indicating that the rate for the overall exchange reaction may be determined by the rate of formation and dissociation of the binuclear complex. The activation energy for the outer-sphere model calculated from the Marcus model is nearly the same as that obtained by a direct calculation of the precursor- and transition-state energy. A simple model with one water ligand is shown to recover 60% of the reorganization energy. This finding is important because it indicates the possibility to carry out theoretical studies of electron-transfer reactions involving M3+ and M4+ actinide species that have eight or nine water ligands in the first coordination sphere.

  • 21.
    Privalov, Timofei
    et al.
    KTH, Superseded Departments, Chemistry.
    Plashkevych, O
    Gel'mukhanov, Faris
    KTH, Superseded Departments, Biotechnology.
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    Continuum modeling of multi-mode vibronic excitations in near-edge x-ray absorption fine structure spectra2000In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 113, no 9, p. 3734-3740Article in journal (Refereed)
    Abstract [en]

    The shape of electro-vibrational bands in near-edge x-ray absorption fine structure (NEXAFS) spectra is often made up by a few strong lines near a phononless resonance. In addition-as predicted here-there can be extended tails due to the large density of vibrational states in the short-wavelength region of the x-ray spectrum where the spacings between vibrational levels are smaller than the lifetime broadening. We propose a continuum approach for simulating vibronic bands in x-ray absorption spectra for systems with a high density of states. This approach is found to provide an accurate description of the spectral shape of the multi-mode vibrational bands in the NEXAFS spectra of polyenes having even a relatively small number of vibrational modes. Ab initio simulations using the discrete linear coupling model confirm the common trends obtained by the continuum approach.

  • 22.
    Privalov, Timofei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Samec, Joseph S. M.
    Backvall, Jan- E.
    DFT study of an inner-sphere mechanism in the hydrogen transfer from a hydroxycyclopentadienyl ruthenium hydride to imines2007In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 26, no 11, p. 2840-2848Article in journal (Refereed)
    Abstract [en]

    A combination of the DFT method with the computational description of environmental effects by solvent was applied to a theoretical study of the hydrogen transfer to imines by [2,3,4,5-Ph-4(eta(5)-C4COH)Ru(CO)(2)H] (2) within a molecular model that closely mimics the authentic reaction conditions. A consistent polarizable continuum solvent model (PCM) was instrumental and necessary in achieving stability of the computational model. Environmental effects by solvent were also considered in an extended model with an addition of explicit solvent molecules within the PCM. The study elucidates an inner-sphere mechanism in detail. Intermediate complexes and transition states are characterized. Three distinct energy barriers along the reaction coordinate are predicted when solvent effects are taken into account. The imine coordinates to ruthenium via ring slippage with an energy barrier of about 15 kcal/mol. Close in energy (12 kcal/mol) is the transition state of the hydride transfer, which gives an (eta(2)-cyclopentadienone)ruthenium amine intermediate. The presence of Ph groups on the Cp ring facilitates the ring slippage that occurs on imine coordination. This eta(2)-intermediate finally rearranges to the corresponding (eta(4)-cyclopentadienone)ruthenium amine complex via a transition state at 9 kcal/mol. The stable ruthenium amine complex was verified against an X-ray structure of the corresponding complex. Inclusion of the solvent (by PCM or explicit molecules) was required to stabilize low-hapticity intermediates and transition state structures.

  • 23.
    Privalov, Timofei
    et al.
    KTH, Superseded Departments, Chemistry.
    Schimmelpfennig, B.
    Wahlgren, U.
    Grenthe, I.
    Reduction of uranyl(VI) by iron(II) in solutions: An ab initio study2003In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 107, no 4, p. 587-592Article in journal (Refereed)
    Abstract [en]

    The reduction of uranyl U(VI) by Fe(II) in solution has been studied by quantum chemical methods, where the pH dependence of the reaction was simulated by using different numbers of coordinated hydroxide ions. The geometries for the binuclear U(VI)-Fe(II) precursor and the U(V)-Fe(III) successor complexes were optimized at the SCF level, and the reaction energies were calculated at the correlated level using the MP2 method. Effective core potentials were used throughout. Solvent effects were obtained by the polarizable continuum model. The accuracy of the solvent model was investigated for the binuclear complexes with two hydroxide bridges, and the accuracy of the MP2 method was assessed by comparing with CASPT2 and CCSD(T) calculations on the smallest complexes. The general trends in geometry and reaction energy are consistent with experiment.

  • 24. Privalov, Timofei
    et al.
    Schimmelpfennig, B.
    Wahlgren, U.
    Grenthe, I.
    Structure and thermodynamics of uranium(VI) complexes in the gas phase: A comparison of experimental and ab initio data2002In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 106, no 46, p. 11277-11282Article in journal (Refereed)
    Abstract [en]

    Ab initio methods were applied for the calculation of the total energy and the molar entropy and heat capacity of the compounds UO2F2, UO2(OH)(2), UF6, and UO3 in the gas phase with the purpose to obtain thermodynamic data for reactions that can be compared with experimental values. The total energy, geometry, and vibration frequencies were calculated at different levels of accuracy: second-order perturbation theory (MP2), coupled cluster theory (CCSD(T)), and density functional theory (B3LYP). Our results agree well with experimental values and previous theoretical results. Additionally, the transition state Of UO2F2(g) was studied and the value of the barrier for the inversion of the fluoride atoms was calculated.

  • 25.
    Privalov, Timofei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Sun, Licheng
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Akermark, Bjorn
    Liu, Jianhui
    Gao, Yan
    Wang, Mei
    A computational study of O-O bond formation catalyzed by monoand Bis-Mn-IV-Corrole complexes2007In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 46, no 17, p. 7075-7086Article in journal (Refereed)
    Abstract [en]

    A detailed computational study of O-O bond formation, catalyzed by monomeric and dimeric Mn-corrole complexes, is reported. The model explicitly takes into account the solvent, with respect to the first and second coordination spheres, while the bulk solvent is described by the polarizable continuum model. Two reaction mechanisms are proposed and computationally characterized: the concerted and the two-step mechanisms. The concerted mechanism is based on a OH--(MnO)-O-IV interaction via the outer-sphere pathway involving the bridging solvent molecules in the first coordinating sphere. The two-step mechanism is proposed to operate via the coordination of a hydroxide to the Mn-Iv ion, forming a MnO(OH)(-)-corrole complex with a strongly nonplanar corrole ligand. Comparison of the proposed mechanisms with available experimental data. is performed.

  • 26.
    Salek, Pawel
    et al.
    KTH, Superseded Departments, Biotechnology.
    Gel'mukhanov, Faris
    KTH, Superseded Departments, Biotechnology.
    Privalov, Timofei
    KTH, Superseded Departments, Biotechnology.
    Ågren, Hans
    KTH, Superseded Departments, Biotechnology.
    Doppler effect for bound nuclear motion and its manifestation in resonant photoemission of oriented systems2000In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 328, no 4-6, p. 425-430Article in journal (Refereed)
    Abstract [en]

    In contrast to the common notion that Doppler effects have relevance only for atoms or molecules in free motion, we show that such effects should clearly be observable - and accounted for - in resonant scattering also when the nuclei are in bound state quantized motion. This untrivial effect does not influence the position of single resonances but only the center of gravity of the spectra. It is found to strongly depend on the duration time of the scattering.

  • 27. Samec, Joseph S. M.
    et al.
    Ell, Alida H.
    Aberg, Jenny B.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Eriksson, Lars
    Backvall, Jan- E.
    Mechanistic study of hydrogen transfer to imines from a hydroxycyclopentadienyl ruthenium hydride. Experimental support for a mechanism involving coordination of imine to ruthenium prior to hydrogen transfer2006In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 128, no 44, p. 14293-14305Article in journal (Refereed)
    Abstract [en]

    Reaction of [2,3,4,5-Ph-4(eta(5)-C4COH) Ru(CO)(2)H] (2) with different imines afforded ruthenium amine complexes at low temperatures. At higher temperatures in the presence of 2, the complexes decomposed to give [Ru-2(CO)(4)(mu-H)(C4Ph4COHOCC4Ph4)] (1) and free amine. Electron-rich imines gave ruthenium amine complexes with 2 at a lower temperature than did electron-deficient imines. The negligible deuterium isotope effect (k(RuHOH)/k(RuDOD) = 1.05) observed in the reaction of 2 with N-phenyl[1-(4-methoxyphenyl) ethylidene]amine (12) shows that neither hydride (RuH) nor proton (OH) is transferred to the imine in the rate-determining step. In the dehydrogenation of N-phenyl-1-phenylethylamine (4) to the corresponding imine 8 by [2,3,4,5-Ph-4(eta(4)-C4CO) Ru(CO)(2)] (A), the kinetic isotope effects observed support a stepwise hydrogen transfer where the isotope effect for C-H cleavage (k(CHNH)/k(CDNH) = 3.24) is equal to the combined (C-H, N-H) isotope effect (k(CHNH)/k(CDND) = 3.26). Hydrogenation of N-methyl(1-phenylethylidene) amine (14) by 2 in the presence of the external amine trap N-methyl-1-(4-methoxyphenyl) ethylamine (16) afforded 90-100% of complex [2,3,4,5-Ph-4(eta(4)-C4CO)] Ru(CO)(2)NH(CH3)(CHPhCH3) (15), which is the complex between ruthenium and the amine newly generated from the imine. At -80 degrees C the reaction of hydride 2 with 4-BnNHsC(6)H(9)=NPh (18), with an internal amine trap, only afforded [2,3,4,5-Ph-4(eta(4)-C4CO)](CO)(2)RuNH(Ph)(C6H10-4-NHBn) (19), where the ruthenium binds to the amine originating from the imine, showing that neither complex A nor the diamine is formed. Above -8 degrees C complex 19 rearranged to the thermodynamically more stable [Ph-4(eta(4)-C4CO)](CO)(2)RuNH(Bn)(C6H10-4-NHPh) (20). These results are consistent with an inner sphere mechanism in which the substrate coordinates to ruthenium prior to hydrogen transfer and are difficult to explain with the outer sphere pathway previously proposed.

  • 28. Schimmelpfennig, B.
    et al.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    Wahlgren, U.
    Grenthe, I.
    Ab initio studies of Np and Pu complexes and reactions in the gas phase: Structures and thermodynamics2003In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 107, no 45, p. 9705-9711Article in journal (Refereed)
    Abstract [en]

    Reaction enthalpies for the reactions 2MO(3)(g) + MF6(g) --> 3MO(2)F(2)(g), MO2F2(9) + 2H(2)O(g) --> MO2(OH)(2)(g) + 2HF(g), MF6(g) + 2H(2)O(g) --> MO2F2(9) + 4HF(g), MO3(g) + H2O(g) --> MO2(OH)(2)(g), and MF6(g) + 3H(2)O (9) --> MO3(g) + 6HF(g) have been calculated at the CCSD(T) level for M = U and Np and at the MP2 level for M = U, Np, and Pu. The results are compared with previous calculated reaction enthalpies for M = U. The errors in the calculated reaction enthalpies are estimated to be below 20 kJ/mol for Np and about 50 kJ/mol for Pu.

  • 29. Schultz, M. J.
    et al.
    Adler, R. S.
    Zierkiewicz, W.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Sigman, M. S.
    Using mechanistic and computational studies to explain ligand effects in the palladium-catalyzed aerobic oxidation of alcohols2005In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 127, no 23, p. 8499-8507Article in journal (Refereed)
    Abstract [en]

    The experimental and computational mechanistic details of the Pd(OAc)(2)/TEA-catalyzed aerobic alcohol oxidation system are disclosed. Measurement of various kinetic isotope effects and the activation parameters as well as rate law derivation support rate-limiting deprotonation of the palladium-coordinated alcohol. Rate-limiting deprotonation of the alcohol is contrary to the majority of related kinetic studies for Pd-catalyzed aerobic oxidation of alcohols, which propose rate-limiting beta-hydride elimination. This difference in the rate-limiting step is supported by the computational model, which predicts the activation energy for deprotonation is 3 kcal/mol higher than the activation energy for beta-hydride elimination. The computational features of the similar Pd(OAc)(2)/pyridine system were also elucidated. Details of the study illustrate that the use of TEA results in an active catalyst that has only one ligand bound to the Pd, resulting in a significant lowering of the activation energy for beta-hydride elimination and, therefore, a catalyst that is active at room temperature.

  • 30. Toraishi, T.
    et al.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    Schimmelpfennig, B.
    Wahlgren, U.
    Grenthe, I.
    Mechanisms of ligand exchange reactions, A quantum chemical study of the reaction UO22+(Aq)+HF(Aq) -> UO2F+(Aq)+H+(Aq)2003In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 107, no 44, p. 9456-9462Article in journal (Refereed)
    Abstract [en]

    The thermodynamics and the reaction mechanism for the reaction UO22+(aq) + HF(aq) --> UO2F+(aq) + H+(aq) in water solution has been studied using quantum chemical methods. The solvent was modeled using the polarized medium method (CPCM) with additional water molecules in the second coordination sphere of the complexes studied. The overall reaction was divided into three steps that were analyzed separately. The quantum chemical study was made on the reaction step [UO2(H2O)(5)(2+)],HF(H2O)(n) --> [UO2F (H2O)(4)(+)],H3O+ (H2O)(n), with n = 1 and 2, where the species in the second coordination sphere are located outside the square brackets. The formation of the precursor complex and dissociation of the successor complex were described by the Fuoss equation. The geometry of the different precursor and successor complexes was in good agreement with known bond distances, and strong F---H---O, and/or O---H---O hydrogen bonds are an important structure element in all of them. The Gibbs energy, enthalpy, and entropy of reaction was calculated using the electronic energy at the MP2 level in the solvent, with thermal functions calculated at the SCF/B3LYP levels using the gas-phase geometry. The calculated Gibbs energy of reaction for n = 2 at 298.15 K was -35 kJ/moI at the HF and -25 kJ/moI at the B3LYP level after correction for a known systematic error in the HF bond energy; this compares favorably with the experimental value, -11 kJ/mol. The ligand exchange mechanism was explored by identification of a transition state where HF from the second sphere enters the first coordination sphere in an associative reaction. It was not possible to identify the same transition state from the successor side, indicating that the reaction mechanism consists of at least two steps. We suggest that the rate determining step is the entry of HF from the second to the first coordination sphere, with practically no bond-breaking as indicated by the small change in the H-F distance between precursor and transition state. This suggestion is supported by the experimentally observed reverse H/D isotope effect. The quantum chemical activation energy DeltaU(not equal) was 34 kJ/mol, close to the experimental activation enthalpy DeltaH(not equal) = 38 kJ/mol.

  • 31. Vallet, V.
    et al.
    Privalov, Timofei
    KTH, Superseded Departments, Chemistry.
    Wahlgren, U.
    Grenthe, Ingmar
    KTH, Superseded Departments, Chemistry.
    The mechanism of water exchange in AmO2(H2O)(5)(2+) and in the isoelectronic UO2(H2O)(5)(+) and NpO2(H2O)(5)(2+) complexes as studied by quantum chemical methods2004In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 126, no 25, p. 7766-7767Article in journal (Refereed)
  • 32. Vastila, P.
    et al.
    Zaitsev, A. B.
    Wettergren, J.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Adolfsson, H.
    The importance of alkali cations in the {RuCl2(p-cymene)}(2) -pseudodipeptide-catalyzed enantioselective transfer hydrogenation of ketones2006In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 12, no 12, p. 3218-3225Article in journal (Refereed)
    Abstract [en]

    We studied the role of alkali cations in the [{RuCl2(p-cymene)}2]- pseudo-dipeptide-catalyzed enantioselective transfer hydrogenation of ketones with isopropanol. Lithium salts were shown to increase the enantioselectivity of the reaction when iPrONa or iPrOK was used as the base. Similar transfer-hydrogenation systems that employ chiral amino alcohol or monotosylated diamine ligands are not affected by the addition of lithium salts. These observations have led us to propose that an alternative reaction mechanism operates in pseudo-dipeptidebased systems, in which the alkali cation is an important player in the ligand-assisted hydrogen-transfer step. DFT calculations of the proposed transition-state (TS) models involving different cations (Li+, Na+, and K+) confirm a considerable loosening of the TS with larger cations. This loosening may be responsible for the fewer interactions between the substrate and the catalytic complex, leading to lower enantiodifferentiation. This mechanistic hypothesis has found additional experimental support; the low ee obtained with [BnNMe3]OH (a large cation) as base can be dramatically improved by introducing lithium cations into the system. Also, the complexation of Na+, K+, and Li+ cations by the addition of [15]crown-5 and [18]crown-6 ethers and cryptand 2.1.1 (which selectively bind to these cations and, thus, increase their bulkiness), respectively, to the reaction mixture led to a significant drop in the enantioselectivity of the reaction. The lithium effect has proved useful for enhancing the reduction of different aromatic and heteroaromatic ketones.

  • 33.
    Zalubovskis, Raivis
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Bouet, Alexis
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Fjellander, Ester
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Constant, Samuel
    University of Geneva.
    Linder, David
    University of Geneva.
    Andreas, Fischer
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry (closed 20110630).
    Lacour, Jérôme
    University of Geneva.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Self-adaptable Catalysts: Substrate-Dependent Ligand Configuration2008In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 130, no 6, p. 1845-1855Article in journal (Refereed)
    Abstract [en]

    Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5dihydro-3H-dibenzo[c-e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic alkylations. According to NMR and DFT studies, the ligand prefers C-s conformation in both eta(3)-1,3-diphenylpropenyl and eta(3)-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different conformations in complexes derived from the two types of allyl systems in both solution and, as verified by X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of adapting its structure to the reacting substrate. The different structural preferences also provide an explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed allylic alkylations using pseudo-C-2 and pseudo-C-s symmetric ligands.

  • 34. Zierkiewicz, W.
    et al.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    A computational study of oxidation of ruthenium porphyrins via ORuIV and (ORuO)-O-VI species2006In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, no 15, p. 1867-1874Article in journal (Refereed)
    Abstract [en]

    An unrestricted density functional theory (UDFT) was applied to study the oxidation of ruthenium porphyrins, [RuP], via an interaction with molecular oxygen. The important role of dimeric [ RuP] complexes, i.e. [RuP]-O-2-[RuP], in the oxidation mechanism and particular in the cleavage of O-O bond of molecular oxygen has been studied. Geometries and relative Gibbs free energies of the intermediate Ru-complexes, i.e. dimeric oxo-Ru-porphyrins and O2RuII-(or O-2(-) Ru-III)-, ORuIV- and (ORuO)-O-VI-porphyrins, were evaluated along the proposed reaction pathway. The detailed thermodynamic data of the oxidation reaction [(RuP)-P-II] -> O[(RuP)-P-IV] -> O[(RuP)-P-VI]O and important aspects of the vibrational spectra of an oxo-[RuP] has been presented.

  • 35. Zierkiewicz, W.
    et al.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    A theoretical study of the essential role of DMSO as a solvent/ligand in the Pd(OAc)(2)/DMSO catalyst system for aerobic oxidation2005In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 24, no 24, p. 6019-6028Article in journal (Refereed)
    Abstract [en]

    Dimethyl sulfoxide (DMSO) has unique properties as an aprotic, polar solvent. The oxygen atom in DMSO can interact with positive charges and thus stabilize metal cation. The sulfur atom, although somewhat positively charged, does not interact with negative charges effectively. Also, two methyl groups surround the sulfur atom and influence binding properties of DMSO. These features of DMSO are addressed in the present computational study of the Pd(AcO)(2)/DMSO-catalyzed aerobic oxidation system. Mechanistic and computational details are provided. The step-by-step Gibbs energy of reaction was calculated using the electronic energy at the B3LYP density functional level with thermal functions calculated at the same level of theory. The solvent was modeled using the polarized medium (PCM) with additional DMSO molecules in the second coordination sphere of the complexes studied. The overall reaction pathway was divided into several steps in accord with available experimental data. All steps, including the first deprotonation and the beta-hydride elimination transition states, were elucidated in good detail. Coordination and reorganization of DMSO in Pd(II)(AcO)(2)/DMSO and Pd(0)/(DMSO)(n) complexes has been studied to provide realistic data about coordination of DMSO with hard (O) versus soft (S) ligand donor atoms. The P-hydride elimination transition state was identified computationally to give an estimation of the activation energy of the alcohol oxidation reaction. Therefore, we suggest that the rate-determining step is related to the alcohol part of the reaction cycle.

1 - 35 of 35
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