Kersti Hermansson

Atomic and electronic structure of unreduced and reduced CeO2 surfaces: A first-principles study

The atomic and electronic structure of (111), (110), and (100) surfaces of ceria (CeO2) were studied using density-functional theory within the generalized gradient approximation. Both stoichiometric surfaces and surfaces with oxygen vacancies (unreduced and reduced surfaces, respectively) have been examined. It is found that the (111) surface is the most stable among the considered surfaces, followed by (110) and (100) surfaces, in agreement with experimental observations and previous theoretical results. Different features of relaxation are found for the three surfaces. While the (111) surface undergoes very small relaxation, considerably larger relaxations are found for the (110) and (100) surfaces. The formation of an oxygen vacancy is closely related to the surface structure and occurs more easily for the (110) surface than for (111). The preferred vacancy location is in the surface layer for CeO2(110) and in the subsurface layer (the second O-atomic layer) for CeO2(111). For both surfaces, the O vacancy forms more readily than in the bulk. An interesting oscillatory behavior is found for the vacancy formation energy in the upper three layers of CeO2(111). Analysis of the reduced surfaces suggests that the additional charge resulting from the formation of the oxygen vacancies is localized in the first three layers of the surface. Furthermore, they are not only trapped in the 4f states of cerium.

Tuning LDA+U for electron localization and structure at oxygen vacancies in ceria.

We examine the real space structure and the electronic structure (particularly Ce4f electron localization) of oxygen vacancies in CeO(2) (ceria) as a function of U in density functional theory studies with the rotationally invariant forms of the LDA+U and GGA+U functionals. The four nearest neighbor Ce ions always relax outwards, with those not carrying localized Ce4f charge moving furthest. Several quantification schemes show that the charge starts to become localized at U approximately 3 eV and that the degree of localization reaches a maximum at approximately 6 eV for LDA+U or at approximately 5.5 eV for GGA+U. For higher U it decreases rapidly as charge is transferred onto second neighbor O ions and beyond. The localization is never into atomic corelike states; at maximum localization about 80-90% of the Ce4f charge is located on the two nearest neighboring Ce ions. However, if we look at the total atomic charge we find that the two ions only make a net gain of (0.2-0.4)e each, so localization is actually very incomplete, with localization of Ce4f electrons coming at the expense of moving other electrons off the Ce ions. We have also revisited some properties of defect-free ceria and find that with LDA+U the crystal structure is actually best described with U=3-4 eV, while the experimental band structure is obtained with U=7-8 eV. (For GGA+U the lattice parameters worsen for U>0 eV, but the band structure is similar to LDA+U.) The best overall choice is U approximately 6 eV with LDA+U and approximately 5.5 eV for GGA+U, since the localization is most important, but a consistent choice for both CeO(2) and Ce(2)O(3), with and without vacancies, is hard to find.

Development and validation of a ReaxFF reactive force field for Cu-cation/water interactions and copper metal/metal oxide/metal hydroxide condensed phases

To enable large-scale reactive dynamic simulations of copper oxide/water and copper ion/water interactions we have extended the ReaxFF reactive force field framework to Cu/O/H interactions. To this end, we employed a multistage force field development strategy, where the initial training set (containing metal/metal oxide/metal hydroxide condensed phase data and [Cu(H(2)O)(n)](2+) cluster structures and energies) is augmented by single-point quantum mechanices (QM) energies from [Cu(H(2)O)(n)](2+) clusters abstracted from a ReaxFF molecular dynamics simulation. This provides a convenient strategy to both enrich the training set and to validate the final force field. To further validate the force field description we performed molecular dynamics simulations on Cu(2+)/water systems. We found good agreement between our results and earlier experimental and QM-based molecular dynamics work for the average Cu/water coordination, Jahn-Teller distortion, and inversion in [Cu(H(2)O)(6)](2+) clusters and first- and second-shell O-Cu-O angular distributions, indicating that this force field gives a satisfactory description of the Cu-cation/water interactions. We believe that this force field provides a computationally convenient method for studying the solution and surface chemistry of metal cations and metal oxides and, as such, has applications for studying protein/metal cation complexes, pH-dependent crystal growth/dissolution, and surface catalysis.

On the nature of blueshifting hydrogen bonds: Ab initio and density functional studies of several fluoroform complexes

Potential energy hypersurfaces (PESs) for four fluoroform complexes (with acetonitrile, ethyleneoxide, formaldehyde, and water) were explored at the HF, MP2, and B3LYP/6-311++G(d,p) levels of theory. Anharmonic C–H stretching vibrational frequency shifts are reported for all minima located on the studied PESs. In all cases, the lowest-energy minimum occurs for a C–H⋯O(N) hydrogen-bonded arrangement and is characterized by a significant C–H frequency blueshift (upshift), while additional minima [for “reversed” orientations, in which there is no direct C–H⋯O(N) contact] show only small C–H frequency upshifts. The large blueshifts found for the hydrogen-bonded arrangements are predominantly caused by the electronic exchange interaction, as revealed by Kitaura–Morokuma (KM) analysis, while the purely electrostatic+polarization interaction leads to C–H frequency redshifts, which was proven both by the KM analysis and the charge field perturbational (CFP) approach. The large net blueshifting effect of the excha...

Contact ion pair formation and ether oxygen coordination in the polymer electrolytes M[N(CF3SO2)2]2PEOn for M = Mg, Ca, Sr and Ba

The polymer electrolytes M[N(CF3SO2)2]2PEOn for M = Mg, Ca, Sr and Ba have been investigated using infra-red spectroscopy, differential scanning calorimetry and impedance spectroscopy. The effects of varying concentration (n = 6–40) and temperature (25–95°C) on the contact ion pair formation and cation coordination have been studied. Contact ion pairs are only found for the most concentrated samples (n < 9). Ion pairs occur with two types of structures: one type is found for samples containing Mg2+ and the other for samples with Ca2+, Sr2+ and Ba2+. The conductivities of the samples are discussed in terms of radii and coordination numbers of the cations.

Oxygen vacancy formation energy in Pd-doped ceria: A DFT+U study

Using the DFT+U method, i.e., first principles density functional theory calculations with the inclusion of on-site Coulomb interaction, the effects of Pd doping on the O vacancy formation energy (E(vac)) in CeO(2) has been studied. We find that E(vac) is lowered from 3.0 eV in undoped ceria to 0.6 eV in the Pd-doped compound. Much of this decrease can be attributed to emerging Pd-induced gap states above the valence band and below the empty Ce 4f states. These localized defect states involve the Pd ion and its nearest neighbors, which are also the main acceptors of the extra electrons left on reduction. The effect of the Pd dopant on the geometric structure is very modest for CeO(2) but considerable for CeO(2-x).

THE OH VIBRATIONAL-SPECTRUM OF LIQUID WATER FROM COMBINED ABINITIO AND MONTE-CARLO CALCULATIONS

The infrared vibrational OH stretching spectrum of isotopically isolated HDO molecules in liquid water has been calculated by ab initio methods at the MP2 level for a number of geometrical configurations taken from a Monte Carlo simulation. Each vibrating water molecule with its environment was described by a pentamer supermolecule, surrounded by a large number of point charges representing polarized water molecules. The anharmonic stretching potentials (MP2 force constants up to fifth order) for 40 uncoupled OH water vibrators were calculated. The average computed re distance found for liquid water is 0.01 A longer than the free‐water value. The frequencies were obtained by solving the one‐dimensional Schrodinger equation variationally for each OH potential curve. Using the squared dipole moment derivatives, which vary by a factor of 7 over the frequency band, the density‐of‐states histograms were converted to intensities. The resulting computed average frequency downshift is ∼260 cm−1, compared to ∼310 ...

ABINITIO CALCULATIONS OF THE FUNDAMENTAL OH FREQUENCY OF BOUND OH- IONS

In contrast to the OH stretching frequencies of bound H2O molecules, which are always found at lower wave numbers compared to the free molecule, the experimentally determined frequency of the OH− ion can be either lower or higher than the free‐ion value. Optimized geometries and fundamental stretching frequency of OH− have been calculated here by ab initio methods at the Hartree–Fock and second‐order Mo/ller–Plesset levels for a number of cation–OH−, HOH⋅⋅⋅OH−, cation–OH−⋅q−, and cation–OH−⋅OH2 complexes for Li+, Mg2+, and Al3+. The importance of electrostatic effects on the OH− frequency has been assessed by comparison with calculations of different point‐charge and homogenous‐field OH− systems. As long as the interaction is not dominated by electronic overlap, the frequency shift is found to be largely determined by electrostatic forces: with increasing field strength the OH− frequency rises to a maximum and then decreases. The OH− dipole moment and Mulliken charges vary monotonically with the field str...

Many-body potentials for aqueous Li+,Na+,Mg2+, and Al3+: Comparison of effective three-body potentials and polarizable models

Many-body potentials for the aqueous Li(+), Na(+), Mg(2+), and Al(3+) ions have been constructed from ab initio cluster calculations. Pure pair, effective pair, effective three-body, and effective polarizable models were created and used in subsequent molecular dynamics simulations. The structures of the first and second solvation shells were studied using radial distribution functions and angular-radial distribution functions. The effective three-body and polarizable potentials yield similar first-shell structures, while the contraction of the O-O distances between the first and second solvation shells is more pronounced with the polarizable potentials. The definition of the tilt angle of the water molecules around the ions is discussed. When a proper definition is used, it is found that for Li(+), Mg(2+), and Al(3+) the water molecules prefer a trigonal orientation, but for Na(+) a tetrahedral orientation (ion in lone-pair direction) is preferred. The self-diffusion coefficients for the water molecules and the ions were calculated; the ionic values follow the order obtained from experiment, although the simulated absolute values are smaller than experiment for Mg(2+) and Al(3+).

Electric‐field effects on the OH vibrational frequency and infrared absorption intensity for water

The variations of the anharmonic OH frequency and the infrared absorption intensity with field strength have been calculated for the uncoupled OH stretching vibration of a water molecule in a static, homogeneous electric field using ab initio methods at the MP4 level with a nearly saturated basis set. The OH frequency is found to be virtually independent of the field components perpendicular to the vibrating OH bond. For the parallel component, the frequency vs field curve is close to quadratic, with a maximum for a slightly negative (directed from H to O) field strength. The external field perturbation, defined as Vext(E∥,rOH)=Vtot(E∥, rOH)−Vfree(rOH), is found to be closely linear in rOH, except when the field strength E∥ is both large and negative. The linear external force constant is almost perfectly accounted for by the sum of two terms, −E∥⋅dμ∥free/drOH and −1/2⋅E∥⋅∂μ∥induced/∂rOH. These derivatives are quite insensitive to the choice of basis‐set. The ∂μ∥induced/∂rOH derivative is approximately pr...