Chris J Pickard

University College London, Londinium, England, United Kingdom

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Publications (230)1083.01 Total impact

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    Full-text · Dataset · Jan 2016
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    ABSTRACT: Hydrogen sulfides have recently received a great deal of interest due to the record high superconducting temperatures of up to 203 K observed on strong compression of dihydrogen sulfide (H2S). A joint theoretical and experimental study is presented in which decomposition products and structures of compressed H2S are characterized, and their superconducting properties are calculated. In addition to the experimentally known H2S and H3S phases, our first-principles structure searches have identified several energetically competitive stoichiometries that have not been reported previously: H2S3, H3S2, HS2, and H4S3. In particular, H4S3 is predicted to be thermodynamically stable within a large pressure range of 25–113 GPa. High-pressure x-ray diffraction measurements confirm the presence of H3S and H4S3 through decomposition of H2S that emerges at 27 GPa and coexists with residual H2S, at least up to the highest pressure of 140 GPa studied in our experiments. Electron-phonon coupling calculations show that H4S3 has a small Tc of below 2 K, and that H2S is mainly responsible for the observed superconductivity of samples prepared at low temperature (<100 K).
    Full-text · Article · Jan 2016
  • Jerome Cuny · Yu Xie · Chris J Pickard · Ali A Hassanali
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    ABSTRACT: Nuclear magnetic resonance (NMR) spectroscopy is one of the most powerful exper- imental tools to probe the local atomic order of a wide range of solid-state compounds. However, due to the complexity of the related spectra, in particular for amorphous materials, their interpretation in terms of structural information is often challenging. These difficulties can be overcome by combining molecular dynamics simulations to generate realistic structural models with an ab initio evaluation of the corresponding nuclear shielding and quadrupolar coupling tensors. However, due to computational constraints, this approach is limited to relatively small system sizes which, for amor- phous materials, prevents an adequate statistical sampling of the distribution of the local environments that is required to quantitatively describe the system. In this work, we present an approach to efficiently and accurately predict the NMR parameters of very large systems. This is achieved by using a high-dimensional neural-network rep- resentation of NMR parameters that are calculated using an ab initio formalism. To illustrate the potential of this approach, we applied this neural-network NMR (NN- NMR) method on the (17)O and (29)Si quadrupolar coupling and chemical shift parameters of various crystalline silica polymorphs and silica glasses. This approach is, in prin- cipal, general and has the potential to be applied to predict the NMR properties of various materials.
    No preview · Article · Jan 2016 · Journal of Chemical Theory and Computation
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    ABSTRACT: Hydrogen compounds are peculiar as the quantum nature of the proton can crucially affect their structural and physical properties. A remarkable example are the high-pressure phases of H$_2$O, where quantum proton fluctuations favor the symmetrization of the H bond and lower by 30 GPa the boundary between the asymmetric structure and the symmetric one. Here we show that an analogous quantum symmetrization occurs in the recently discovered sulfur hydride superconductor with the record superconducting critical temperature $T_c=203$ K at 155 GPa. In this system, according to classical theory, superconductivity occurs via formation of a structure of stoichiometry H$_3$S with S atoms arranged on a body-centered-cubic (bcc) lattice. For $P \gtrsim 175$ GPa, the H atoms are predicted to sit midway between two S atoms, in a structure with $Im\bar3m$ symmetry. At lower pressures the H atoms move to an off-center position forming a short H$-$S covalent bond and a longer H$\cdots$S hydrogen bond, in a structure with $R3m$ symmetry. X-ray diffraction experiments confirmed the H$_3$S stoichiometry and the S lattice sites, but were unable to discriminate between the two phases. Our present ab initio density-functional theory (DFT) calculations show that the quantum nuclear motion lowers the symmetrization pressure by 72 GPa. Consequently, we predict that the $Im\bar3m$ phase is stable over the whole pressure range within which a high $T_c$ was measured. The observed pressure-dependence of $T_c$ is closely reproduced in our calculations for the $Im\bar3m$ phase, but not for the $R3m$ phase. Thus, the quantum nature of the proton completely rules the superconducting phase diagram of H$_3$S.
    Full-text · Article · Dec 2015
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    ABSTRACT: Binary hydrides formed by the pnictogens of phosphorus, arsenic and antimony are studied at high pressures using first principles methods. Stable structures are predicted and their electronic, vibrational and superconducting properties are investigated. We predict that SbH$_{4}$ and AsH$_{8}$ will be high-temperature superconductors at megabar pressures, with critical temperatures in excess of 100 K. The highly symmetric hexagonal SbH$_{4}$ phase is predicted to be stabilized above about 150 GPa, which is readily achievable in diamond anvil cell experiments. We find that all phosphorus hydrides are metastable with respect to decomposition into the elements within the pressure range studied. Trends based on our results and literature data reveal a connection between the high-pressure behaviors and ambient-pressure chemical quantities which provides insight into understanding which elements may form hydrogen-rich high-temperature superconducting phases at high pressures.
    No preview · Article · Oct 2015
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    ABSTRACT: Selenium-rich Ge-Te-Se glasses have been synthesized along the GeSe4-GeTe4 pseudo-composition line and acquired by (77)Se Hahn echo magic-angle spinning NMR. The comparison with the GeSe4 spectrum shows a drastic modification of the typical double-resonance lineshape even at low Te concentrations (<10%). In order to rationalize this feature and to understand the effect of Te on the structure of our glasses, first-principles molecular dynamics simulations and gauge including projector augmented wave NMR parameter calculations have been performed. The distribution of the tellurium atoms in the selenium phase was shown to be mainly responsible for the (77)Se lineshape changes. Another possible factor related to the perturbation of the δiso value due to Te proximity appears to be much more limited in the bulk, while the results obtained using molecular models suggest shifts of several hundreds of ppm.
    Full-text · Article · Oct 2015 · Physical Chemistry Chemical Physics
  • Martin Mayo · Kent J. Griffith · Chris J. Pickard · Andrew J. Morris
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    ABSTRACT: Phosphorus has received recent attention in the context of high-capacity and high-rate anodes for lithium and sodium-ion batteries. Here, we present a first principles structure prediction study combined with NMR calculations which gives us insights into its lithiation/sodiation process. We report a variety of new phases phases found by AIRSS and the atomic species swapping methods. Of particular interest, a stable Na$_5$P$_4$-C2/m structure and locally stable structures found less than 10 meV/f.u. from the convex hull, such as Li$_4$P$_3$-P2$_1$2$_1$2$_1$, NaP$_5$-Pnma and Na$_4$P$_3$-Cmcm. The mechanical stability of Na$_5$P$_4$-C2/m and Li$_4$P$_3$-P2$_1$2$_1$2$_1$ has been studied by first principles phonon calculations . We have calculated average voltages which suggests that black phosphorus (BP) can be considered as a safe anode in lithium-ion batteries due to its high lithium insertion voltage, 1.5 V; moreover, BP exhibits a relatively low theoretical volume expansion compared with other intercalation anodes, 216\% ($\Delta V/V$). We identify that specific ranges in the calculated shielding can be associated with specific ionic arrangements, results which play an important role in the interpretation of NMR spectroscopy experiments. Since the lithium-phosphides are found to be insulating even at high lithium concentrations we show that Li-P-doped phases with aluminium have electronic states at the Fermi level suggesting that using aluminium as a dopant can improve the electrochemical performance of P anodes.
    No preview · Article · Oct 2015
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    Gihan L. Weerasinghe · R. J. Needs · Chris J. Pickard
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    ABSTRACT: We have used density-functional-theory methods and the ab initio random structure searching (AIRSS) approach to predict stable structures and stoichiometries of mixtures of iron and oxygen at high pressures. Searching was performed for 12 different stoichiometries at pressures of 100, 350 and 500 GPa, which involved relaxing more than 32,000 structures. We find that Fe$_2$O$_3$ and FeO$_2$ are the only phases stable to decomposition at 100 GPa, while at 350 and 500 GPa several stoichiometries are found to be stable or very nearly stable. We report a new structure of Fe$_2$O$_3$ with $P2_12_12_1$ symmetry which is found to be more stable than the known Rh$_2$O$_3$(II) phase at pressures above $\sim$233 GPa. We also report two new structures of FeO, with $Pnma$ and $R\bar{3}m$ symmetries, which are found to be stable within the ranges 195-285 GPa and 285-500 GPa, respectively, and two new structures of Fe$_3$O$_4$ with $Pca2_1$ and $P2_1/c$ symmetries, which are found to be stable within the ranges 100-340 GPa and 340-500 GPa, respectively. Finally, we report two new structures of Fe$_4$O$_5$ with $P4_2/n$ and $P\bar{3}m1$ symmetries, which are found to be stable within the ranges 100-231 GPa and 231-500 GPa, respectively. Our new structures of Fe$_3$O$_4$ and Fe$_4$O$_5$ are found to have lower enthalpies than their known structures within their respective stable pressure ranges.
    Preview · Article · Aug 2015 · Journal of Physics Condensed Matter
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    ABSTRACT: Hydrogen sulfides have recently received a great deal of interest due to the record high superconducting temperatures of up to 203 K observed on strong compression of dihydrogen sulfide (H2S). A joint theoretical and experimental study is presented in which decomposition products of compressed H2S are characterized, and their superconducting properties are calculated. In addition to the experimentally known H2S and H3S phases, our first-principles structure searches have identified several energetically competitive stoichiometries that have not been reported previously; H2S3, H3S2, and H4S3. In particular, H4S3 is predicted to be thermodynamically stable within a large pressure range of 25-113 GPa. High-pressure room-temperature X-ray diffraction measurements confirm the presence of an H4S3 phase that emerges at 27 GPa and coexists with H3S and residual H2S, at least up to the highest pressure studied in our experiments of 140 GPa. Electron-phonon coupling calculations show that H4S3 has a small Tc of below 2 K, and that H2S is mainly responsible for the observed superconductivity for samples prepared at low temperature.
    Full-text · Article · Aug 2015
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    ABSTRACT: Despite relevance to disparate areas such as cloud microphysics and tribology, major gaps in the understanding of the structures and phase transitions of low-dimensional water ice remain. Here we report a first principles study of confined 2D ice as a function of pressure. We find that at ambient pressure hexagonal and pentagonal monolayer structures are the two lowest enthalpy phases identified. Upon mild compression the pentagonal structure becomes the most stable and persists up to \textit{ca.} 2 GPa at which point square and rhombic phases are stable. The square phase agrees with recent experimental observations of square ice confined within graphene sheets. We also find a double layer AA stacked square ice phase, which clarifies the difference between experimental observations and earlier force field simulations. This work provides a fresh perspective on 2D confined ice, highlighting the sensitivity of the structures observed to both the confining pressure and width.
    Full-text · Article · Aug 2015 · Physical Review Letters
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    ABSTRACT: We present here a first-principles study of the ternary compounds formed by Ni, In, and As, a material of great importance for self-aligned metallic contacts in next-generation InAs-based MOS transistors. The approach we outline is general and can be applied to study the crystal structure and properties of a host of other new interface compounds. Using the ab initio random structure searching approach we find the previously unknown low-energy structures of NixInAs and assess their stability with respect to the known binary compounds of Ni, In, and As. Guided by experiments, we focus on Ni3InAs and find a rich energy landscape for this stoichiometry. We consider the five lowest-energy structures, with space groups Pmmn, Pbcm, P21/m, Cmcm, and R3¯. The five low-energy structures for Ni3InAs are all found to be metallic and nonmagnetic. By comparison to previously published TEM results we identify the crystal structure observed in experiments to be Cmcm Ni3InAs. We calculate the work function for Cmcm Ni3InAs and, according to the Schottky-Mott model, expect the material to form an Ohmic contact with InAs. We further explicitly consider the interface between Cmcm Ni3InAs and InAs and find it to be Ohmic with an n-type Schottky barrier height of -0.55eV. © 2015 authors. Published by the American Physical Society. Published by the American Physical Society under the terms of the Creative Commons Attribution 3.0 License. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.
    No preview · Article · Aug 2015 · Physical Review B
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    ABSTRACT: Establishing the phase diagram of hydrogen is a major challenge for experimental and theoretical physics. Experiment alone cannot establish the atomic structure of solid hydrogen at high pressure, because hydrogen scatters X-rays only weakly. Instead, our understanding of the atomic structure is largely based on density functional theory (DFT). By comparing Raman spectra for low-energy structures found in DFT searches with experimental spectra, candidate atomic structures have been identified for each experimentally observed phase. Unfortunately, DFT predicts a metallic structure to be energetically favoured at a broad range of pressures up to 400 GPa, where it is known experimentally that hydrogen is non-metallic. Here we show that more advanced theoretical methods (diffusion quantum Monte Carlo calculations) find the metallic structure to be uncompetitive, and predict a phase diagram in reasonable agreement with experiment. This greatly strengthens the claim that the candidate atomic structures accurately model the experimentally observed phases.
    Preview · Article · Jul 2015 · Nature Communications
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    ABSTRACT: [Mo6X14](2-) octahedral molybdenum clusters are the main building blocks of a large range of materials. Although (95)Mo nuclear magnetic resonance was proposed to be a powerful tool to characterize their structural and dynamical properties in solution, these measurements have never been complemented by theoretical studies which can limit their interpretation for complex systems. In this Article, we use quantum chemical calculations to evaluate the (95)Mo chemical shift of three clusters: [Mo6Cl14](2-), [Mo6Br14](2-), and [Mo6I14](2-). In particular, we test various computational parameters influencing the quality of the results: size of the basis set, treatment of relativistic and solvent effects. Furthermore, to provide quantum chemical calculations that are directly comparable with experimental data, we evaluate for the first time the (95)Mo nuclear magnetic shielding of the experimental reference, namely, MoO4(2-) in aqueous solution. This is achieved by combining ab initio molecular dynamics simulations with a periodic approach to evaluate the (95)Mo nuclear shieldings. The results demonstrate that, despite the difficulty to obtain accurate (95)Mo chemical shifts, relative values for a cluster series can be fairly well-reproduced by DFT calculations. We also show that performing an explicit solvent treatment for the reference compound improves by ∼50 ppm the agreement between theory and experiment. Finally, the standard deviation of ∼70 ppm that we calculate for the (95)Mo nuclear shielding of the reference provides an estimation of the accuracy we can achieve for the calculation of the (95)Mo chemical shifts using a static approach. These results demonstrate the growing ability of quantum chemical calculations to complement and interpret complex experimental measurements.
    No preview · Article · Jul 2015 · Inorganic Chemistry
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    ABSTRACT: Ordinary materials can transform into novel phases at extraordinary high pressure and temperature. The recently developed method of ultrashort laser-induced confined microexplosions initiates a non-equilibrium disordered plasma state. Ultra-high quenching rates overcome kinetic barriers to the formation of new metastable phases, which are preserved in the surrounding pristine crystal for subsequent exploitation. Here we demonstrate that confined microexplosions in silicon produce several metastable end phases. Comparison with an ab initio random structure search reveals six energetically competitive potential phases, four tetragonal and two monoclinic structures. We show the presence of bt8 and st12, which have been predicted theoretically previously, but have not been observed in nature or in laboratory experiments. In addition, the presence of the as yet unidentified silicon phase, Si-VIII and two of our other predicted tetragonal phases are highly likely within laser-affected zones. These findings may pave the way for new materials with novel and exotic properties.
    Full-text · Article · Jun 2015 · Nature Communications
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    Andrés Mujica · Chris J. Pickard · Richard J. Needs
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    ABSTRACT: Searches for low-energy tetrahedral polymorphs of carbon and silicon have been performed using density functional theory computations and the ab initio random structure searching approach. Several of the hypothetical phases obtained in our searches have enthalpies that are lower or comparable to those of other polymorphs of group 14 elements that have either been experimentally synthesized or recently proposed as the structure of unknown phases obtained in experiments, and should thus be considered as particularly interesting candidates. A structure of $Pbam$ symmetry with 24 atoms in the unit cell was found to be a low-energy, low-density metastable polymorph in carbon, silicon, and germanium. In silicon, $Pbam$ is found to have a direct band gap at the zone center with an estimated value of 1.4 eV, which suggests applications as a photovoltaic material. We have also found a low-energy chiral framework structure of $P{4}_{1}{2}_{1}2$ symmetry with 20 atoms per cell containing fivefold spirals of atoms, whose projected topology is that of the so-called Cairo-type two-dimensional pentagonal tiling. We suggest that $P{4}_{1}{2}_{1}2$ is a likely candidate for the structure of the unknown phase XIII of silicon. We discuss $Pbam$ and $P{4}_{1}{2}_{1}2$ in detail, contrasting their energetics and structures with those of other group 14 elements, particularly the recently proposed $P{4}_{2}/ncm$ structure, for which we also provide a detailed interpretation as a network of tilted diamondlike tetrahedra.
    Preview · Article · Jun 2015 · Physical Review B
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    Matthew J Lyle · Chris J Pickard · Richard J Needs
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    ABSTRACT: We predict by first-principles methods a phase transition in TiO2 at 6.5 Mbar from the Fe2P-type polymorph to a ten-coordinated structure with space group I4/mmm. This is the first report, to our knowledge, of the pressure-induced phase transition to the I4/mmm structure among all dioxide compounds. The I4/mmm structure was found to be up to 3.3% denser across all pressures investigated. Significant differences were found in the electronic properties of the two structures, and the metallization of TiO2 was calculated to occur concomitantly with the phase transition to I4/mmm. The implications of our findings were extended to SiO2, and an analogous Fe2P-type to I4/mmm transition was found to occur at 10 TPa. This is consistent with the lower-pressure phase transitions of TiO2, which are well-established models for the phase transitions in other AX2 compounds, including SiO2. As in TiO2, the transition to I4/mmm corresponds to the metallization of SiO2. This transformation is in the pressure range reached in the interiors of recently discovered extrasolar planets and calls for a reformulation of the equations of state used to model them.
    Full-text · Article · May 2015 · Proceedings of the National Academy of Sciences
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    ABSTRACT: We use first-principles calculations to study structural, vibrational, and superconducting properties of H_{2}S at pressures P≥200 GPa. The inclusion of zero-point energy leads to two different possible dissociations of H_{2}S, namely 3H_{2}S→2H_{3}S+S and 5H_{2}S→3H_{3}S+HS_{2}, where both H_{3}S and HS_{2} are metallic. For H_{3}S, we perform nonperturbative calculations of anharmonic effects within the self-consistent harmonic approximation and show that the harmonic approximation strongly overestimates the electron-phonon interaction (λ≈2.64 at 200 GPa) and T_{c}. Anharmonicity hardens H─S bond-stretching modes and softens H─S bond-bending modes. As a result, the electron-phonon coupling is suppressed by 30% (λ≈1.84 at 200 GPa). Moreover, while at the harmonic level T_{c} decreases with increasing pressure, the inclusion of anharmonicity leads to a T_{c} that is almost independent of pressure. High-pressure hydrogen sulfide is a strongly anharmonic superconductor.
    Full-text · Article · Apr 2015 · Physical Review Letters
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    Full-text · Dataset · Apr 2015
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    Yinwei Li · Yanchao Wang · Chris J. Pickard · Richard J. Needs · Yi Wang · Yanming Ma
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    ABSTRACT: Alkali metals exhibit unexpected structures and electronic behavior at high pressures. Compression of metallic sodium (Na) to 200 GPa leads to the stability of a wide-band-gap insulator with the double hexagonal hP4 structure. Post-hP4 structures remain unexplored, but they are important for addressing the question of the pressure at which Na reverts to a metal. Here we report the reentrant metallicity of Na at the very high pressure of 15.5 terapascal (TPa), predicted using first-principles structure searching simulations. Na is therefore insulating over the large pressure range of 0.2-15.5 TPa. Unusually, Na adopts an oP8 structure at pressures of 117-125 GPa, and the same oP8 structure at 1.75-15.5 TPa. Metallization of Na occurs on formation of a stable and striking body-centered cubic cI24 electride structure consisting of Na12 icosahedra, each housing at its center about one electron which is not associated with any Na ions.
    Full-text · Article · Mar 2015 · Physical Review Letters
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    Joseph R Nelson · Richard J Needs · Chris J Pickard
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    ABSTRACT: Structures of calcium peroxide (CaO2) are investigated in the pressure range 0-200 GPa using the ab initio random structure searching (AIRSS) method and density functional theory (DFT) calculations. At 0 GPa, there are several CaO2 structures very close in enthalpy, with the ground-state structure dependent on the choice of exchange-correlation functional. Further stable structures for CaO2 with C2/c, I4/mcm and P21/c symmetries emerge at pressures below 40 GPa. These phases are thermodynamically stable against decomposition into CaO and O2. The stability of CaO2 with respect to decomposition increases with pressure, with peak stability occurring at the CaO B1-B2 phase transition at 65 GPa. Phonon calculations using the quasiharmonic approximation show that CaO2 is a stable oxide of calcium at mantle temperatures and pressures, highlighting a possible role for CaO2 in planetary geochemistry. We sketch the phase diagram for CaO2, and find at least five new stable phases in the pressure-temperature ranges 0 ≤ P ≤ 60 GPa, 0 ≤ T ≤ 600 K, including two new candidates for the zero-pressure ground state structure.
    Preview · Article · Feb 2015 · Physical Chemistry Chemical Physics

Publication Stats

14k Citations
1,083.01 Total Impact Points


  • 2009-2015
    • University College London
      • Department of Physics and Astronomy
      Londinium, England, United Kingdom
    • Fudan University
      • Department of Material Science
      Shanghai, Shanghai Shi, China
  • 2014
    • California Institute of Technology
      Pasadena, California, United States
  • 2013
    • The University of York
      • Department of Physics
      York, England, United Kingdom
  • 2012
    • Utah State University
      • Department of Chemistry and Biochemistry
      Logan, Ohio, United States
  • 1999-2012
    • Christian-Albrechts-Universität zu Kiel
      Kiel, Schleswig-Holstein, Germany
  • 1997-2012
    • University of Cambridge
      • Department of Physics: Cavendish Laboratory
      Cambridge, England, United Kingdom
  • 2007-2010
    • University of St Andrews
      • School of Physics and Astronomy
      Saint Andrews, SCT, United Kingdom
  • 2007-2009
    • Scottish Universities Physics Alliance
      Glasgow, Scotland, United Kingdom
  • 2008
    • Durham University
      • Department of Chemistry
      Durham, England, United Kingdom
  • 2006
    • Max Planck Institute for Solid State Research
      Stuttgart, Baden-Württemberg, Germany
  • 2001
    • Kiel Institute for the Word Economy
      Kiel, Schleswig-Holstein, Germany
    • Tamkang University
      • Department of Chemistry
      T’ai-pei, Taipei, Taiwan