| 1. |
- Sillrén, Per, 1982, et al.
(författare)
-
A statistical model of hydrogen bond networks in liquid alcohols
- 2012
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 1089-7690 .- 0021-9606. ; 136:9, s. 094514-094521
-
Tidskriftsartikel (refereegranskat)abstract
- We here present a statistical model of hydrogen bond induced network structures in liquid alcohols. The model generalises the Andersson-Schulz-Flory chain model to allow also for branched structures. Two bonding probabilities are assigned to each hydroxyl group oxygen, where the first is the probability of a lone pair accepting an H-bond and the second is the probability that given this bond also the second lone pair is bonded. The average hydroxyl group cluster size, cluster size distribution, and the number of branches and leaves in the tree-like network clusters are directly determined from these probabilities. The applicability of the model is tested by comparison to cluster size distributions and bonding probabilities obtained from Monte Carlo simulations of the monoalcohols methanol, propanol, butanol, and propylene glycol monomethyl ether, the di-alcohol propylene glycol, and the tri-alcohol glycerol. We find that the tree model can reproduce the cluster size distributions and the bonding probabilities for both mono- and poly-alcohols, showing the branched nature of the OH-clusters in these liquids. Thus, this statistical model is a useful tool to better understand the structure of network forming hydrogen bonded liquids. The model can be applied to experimental data, allowing the topology of the clusters to be determined from such studies.
|
|
| 2. |
- Bielecki, Johan, 1982, et al.
(författare)
-
Femtosecond optical reflectivity measurements of lattice-mediated spin repulsions in photoexcited LaCoO3 thin films
- 2014
-
Ingår i: Physical Review B - Condensed Matter and Materials Physics. - 2469-9950 .- 2469-9969 .- 1098-0121 .- 1550-235X. ; 89:3, s. art. no. 035129-
-
Tidskriftsartikel (refereegranskat)abstract
- We present results on the temperature dependence of ultrafast electron and lattice dynamics, measured with pump-probe transient reflectivity experiments, of an epitaxially grown LaCoO3 thin film under tensile strain. Probing spin-polarized transitions into the antibonding e(g) band provides a measure of the low-spin fraction, both as a function of temperature and time after photoexcitation. It is observed that femtosecond laser pulses destabilize the constant low-spin fraction (similar to 63%-64%) in equilibrium into a thermally activated state, driven by a subpicosecond change in spin gap Delta. From the time evolution of the low-spin fraction, it is possible to disentangle the thermal and lattice contributions to the spin state. A lattice mediated spin repulsion, identified as the governing factor determining the equilibrium spin state in thin-film LaCoO3, is observed. These results suggests that time-resolved spectroscopy is a sensitive probe of the spin state in LaCoO3 thin films, with the potential to bring forward quantitative insight into the complicated interplay between structure and spin state in LaCoO3.
|
|
| 3. |
- Bielecki, Johan, 1982, et al.
(författare)
-
Short-range structure of the brownmillerite-type oxide Ba2In2O5 and its hydrated proton-conducting form BaInO3H
- 2014
-
Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry (RSC). - 2050-7488 .- 2050-7496. ; 2:40, s. 16915-16924
-
Tidskriftsartikel (refereegranskat)abstract
- The vibrational spectra and short-range structure of the brownmillerite-type oxide Ba2In2O6 and its hydrated form BaInO3H, are investigated by means of Raman, infrared, and inelastic neutron scattering spectroscopies together with density functional theory calculations. For Ba2In2O6, which may be described as an oxygen deficient perovskite structure with alternating layers of InO6 octahedra and InO4 tetrahedra, the results affirm a short-range structure of Icmm symmetry, which is characterized by random orientation of successive layers of InO4 tetrahedra. For the hydrated, proton conducting, form, BaInO3H, the results suggest that the short-range structure is more complicated than the P4/mbm symmetry that has been proposed previously on the basis of neutron diffraction, but rather suggest a proton configuration close to the lowest energy structure predicted by Martinez et al. [J.-R. Martinez, C. E. Moen, S. Stoelen, N. L. Allan, J. Solid State Chem., 180, 3388, (2007)]. An intense Raman active vibration at 150 cm(-1) is identified as a unique fingerprint of this proton configuration.
|
|
| 4. |
- Bielecki, Johan, 1982, et al.
(författare)
-
Structural and magnetic properties of isovalently substituted multiferroic BiFeO3 : Insights from Raman spectroscopy
- 2012
-
Ingår i: Physical Review B Condensed Matter. - 0163-1829 .- 1095-3795. ; 86:184422
-
Tidskriftsartikel (refereegranskat)abstract
- Raman spectra, supplemented by powder x-ray diffraction and magnetization data of isovalently A- and B-site substituted BiFeO3 in the Bi1−xLaxFeO3 (0≤x≤1), Bi1−xTbxFeO3 (0≤x≤0.2), and Bi0.9Sm0.1Fe1−xMnxO3 (0≤x≤0.3) series, are presented. A good agreement between the structural transitions observed by x-ray diffraction and the vibrational modes observed in the Raman spectra is found over the whole substitutional ranges, and in particular we find spectroscopic signatures of a PbZrO3-type structure for Bi0.8La0.2FeO3. Mode assignments in the substituted materials are made based on Raman spectra of the end-members BiFeO3 and LaFeO3. Moreover, by comparing spectra from all samples with R3c structure, the phonon assignment in BiFeO3 is revisited. A close connection between the degree of octahedral tilt and the Raman shift of the A1 oxygen a−a−a− tilt mode is established. An explanation for the strong second-order scattering observed in Bi1−xLaxFeO3 and Bi1−xTbxFeO3 is suggested, including the assignment of the previously mysterious BiFeO3 mode at 620 cm−1. Finally, the magnetization data indicates a transition from a cycloidal modulated state towards a canted antiferromagnet with increasing A-site substitution, while Bi0.9Sm0.1Fe1−xMnxO3 with x=0 and 0.15 exhibit an anomalous closing of the hysteresis loop at low temperatures. For low A-site substitution levels (x≤0.1) the decreasing Raman intensity of the Fe derived modes correlates with the partial destruction of the spin cycloid as the substitution level increases.
|
|
| 5. |
- Bielecki, Johan, 1982, et al.
(författare)
-
Two-component heat diffusion observed in LaMnO3 and La0.7Ca0.3MnO3
- 2010
-
Ingår i: Physical Review B Condensed Matter. - : Americal Physical Society. - 0163-1829 .- 1095-3795. ; 81:6, s. art. no. 064434-
-
Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- We investigate the low-temperature electron, lattice, and spin dynamics of LaMnO3 (LMO) and La0.7Ca0.3MnO3 (LCMO) by resonant pump-probe reflectance spectroscopy. Probing the high-spin d-d transition as a function of time delay and probe energy, we compare the responses of the Mott insulator and the double-exchange metal to the photoexcitation. Attempts have previously been made to describe the subpicosecond dynamics of colossal magnetoresistance manganites in terms of a phenomenological three-temperature model describing the energy transfer between the electron, lattice, and spin subsystems followed by a comparatively slow exponential decay back to the ground state. However, conflicting results have been reported. Here we first show clear evidence of an additional component in the long-term relaxation due to film-to-substrate heat diffusion and then develop a modified three-temperature model that gives a consistent account for this feature. We confirm our interpretation by using it to deduce the band gap in LMO. In addition, we also model the nonthermal subpicosecond dynamics, giving a full account of all observed transient features both in the insulating LMO and the metallic LCMO.
|
|
| 6. |
- Knee, Christopher, 1973, et al.
(författare)
-
High Pressure Crystal and Magnetic Phase Transitions in Multiferroic Bi0.9La0.1FeO3
- 2014
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 26:2, s. 1180-1186
-
Tidskriftsartikel (refereegranskat)abstract
- The crystal and magnetic structures of multiferroic Bi0.9La0.1FeO3 have been studied using high resolution neutron powder diffraction in the pressure range 0-8 GPa. Two structural phase transitions are observed. The first, at similar to 1 GPa, transforms the polar R3c structure to an antipolar PbZrO3-like root 2a(p) x 2 root 2a(p) x 2a(p) perovskite superstructure; the second, at similar to 5 GPa, results in a smaller, root 2a(p) x root 2a(p) x 2a(p) unit cell and a structure described with Ibmm (nonstandard setting of Imma) symmetry, in which the a(-)a(-)b(0) octahedral tilt system is retained and the antipolar cation displacements lost. Accompanying the changes in the nuclear structure, the antiferromagnetic spin structure evolves from a cycloid, with a modulation length, lambda approximate to 770 angstrom, to collinear arrangements with the moments aligned along the b-axis (Pbam) and the a-axis (Ibmm) of the orthorhombic unit cells. In comparison with BiFeO3 the transition from a rhombohedral to an orthorhombic structure is suppressed by similar to 3 GPa, reflecting the dilution of the stereochemically active bismuth lone pair by lanthanum. A correlation between the cell contraction of Bi1-xLaxFeO3 (0.0
|
|
