Sheng Hsien Lin

National Chiao Tung University, Hsin-chu-hsien, Taiwan, Taiwan

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Publications (129)381.45 Total impact

  • Yu-Hui Liu · Sheng-Cheng Lan · Chaoyuan Zhu · Sheng Hsien Lin
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    ABSTRACT: The dynamics of the excited-state intramolecular proton-transfer (ESIPT) reaction of quinoline-pyrazole (QP) isomers, designated as QP-I and QP-II, has been investigated by means of time-dependent density functional theory (TDDFT). A lower barrier has been found in the potential energy curve for the lowest singlet excited state (S1) along the proton-transfer coordinate of QP-II compared to that of QP-I. However, this is at variance with a recent experimental report [J. Phys. Chem. A 2010, 114, 7886-7891], in which the authors proposed that the ESIPT reaction would only proceed in QP-I due to the absence of a PT emission for QP-II. Therefore, several deactivating pathways have been investigated to determine whether fluorescence quenching occurs in the PT form of QP-II (PT-II). The S1 state of PT-II has nπ* character, which is a well-known dark state. Moreover, the energy gap between the S1 and T2 states is only 0.29 eV, implying that an intersystem crossing (ISC) process would occur rapidly following the ESIPT reaction. Therefore, it is demonstrated that the ESIPT could successfully proceed in QP-II, and that the PT emission would be quenched by the ISC process.
    The Journal of Physical Chemistry A 06/2015; 119(24). DOI:10.1021/acs.jpca.5b03557 · 2.78 Impact Factor
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    ABSTRACT: Control of mobile π-electrons is one of the fundamental issues in the organic optoelectronics for designing the next generation ultrafast switching devices. The optimal control simulations of coherent π-electron rotations in (P)-2,2’-biphenol, which is the typical nonplanar aromatic molecule with axial chirality, were performed by taking into account two types of the control targets: one is generation of the maximum π-angular momentum, and the other is the maintaining of the generated unidirectional angular momentum during a setting time duration. The optimal control pulse for each target is designed. The analysis of the simulation results shows that the effective maintaining of the unidirectional angular momentum can be realized by applying 2π pulse to one of the electronic excited states forming the coherent electronic state. The 2π pulse prevents the reverse rotation of the π-electrons by dumping the excited state population to the ground state and subsequently by pumping the population back to the excited state. The present results provide a theoretical basis for the designing next generation ultrafast switching devices made by organic aromatic molecules.
    05/2015; DOI:10.1002/jccs.201500043
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    ABSTRACT: In this paper, we theoretically and experimentally investigate the photophysical and chemical characteristics and absorption spectra of various ruthenium complexes in solution used as efficient dye-sensitized solar cells. The target molecules are two popular complexes, cis-[Ru(4,4’-COO-2,2’-bpy)2(X)2]4-, (X = NCS, Cl) and trans-terpyridyl Ru. The experimental absorption spectra of these molecules, which show strong spin-orbit (SO) coupling are simulated using first-order perturbation theory based on time-dependent density functional theory and quantum chemistry calculations. It turns out that the theory can simulate the experimental data very well, which indicates that SO coupling is very important and the mixing between singlet and triplet states is strong in these molecules because of the large SO coupling constant of the Ru atom. The exact absorption spectra can only be reproduced by including the perturbation by SO couplings. The physical and chemical differences between cis-[Ru(4,4’-COO-2,2’-bpy)2(X)2]4-, (X = NCS, Cl) and trans-terpyridyl Ru complexes are elucidated using natural bond orbital and natural transition orbital analyses. From these analyses, we have found that the two kinds of Ru complexes are quite different in terms of photoexitation response and chemical bonding between the central Ru atom and the surrounding ligands.
    Physical Chemistry Chemical Physics 04/2015; 17(18). DOI:10.1039/C5CP00984G · 4.20 Impact Factor
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    ABSTRACT: The pressure-dependent interactions between the ionic liquid mixture ([MPI][I1.5]) and nano-TiO2 surfaces have been studied up to 2.5 GPa. The results of infrared spectroscopic profiles of [MPI][I1.5] and [MPI][I1.5]/ nano-TiO2 indicated that no appreciable changes of the C-H stretching bands with the addition of nano-TiO2 were observed under ambient pressure. As the pressure was elevated to 0.7 GPa, the C-H stretching absorption of [MPI][I1.5] underwent band-narrowing and red-shifts in frequency. In contrast to the results of [MPI][I1.5], the spectra of [MPI][I1.5]/ nano-TiO2 do not show dramatic changes under high pressures. A possible explanation for this observation is the formation of certain pressure-enhanced C-H---nano-TiO2 interactions around the imidazolium C-H and alkyl C-H groups. As imidazolium C-H---I- is replaced by the weaker imidazolium C-H---polyiodide, the splitting of the imidazolium C-H stretching bands was observed. The experimental results indicate that both nano-TiO2 and polyiodides are capable of disturbing the self-assembly of ionic liquids. This study suggests the possibility to tune the efficiency of dye-sensitized solar cells via high pressure method.
    Physical Chemistry Chemical Physics 11/2014; DOI:10.1039/C4CP04768K · 4.20 Impact Factor
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    Min‐Yeh Tsai · Jian‐Min Yuan · Sheng‐Hsien Lin
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    ABSTRACT: In this work, we present a kinetic analysis for protein aggregation using the kinetic Ising model, which serves as a new application of a previously proposed model [Liang et al., J. Chin. Chem. Soc.­ 2003, 50, 335]. Considering protein as a single spin unit, we map two states of a unit to the aggregation-prone (AP) and the fibril (F) states. This work shows that the model can successfully capture the nucleation-growth features of protein aggregation from experiments, which offers thermodynamic interpretations of aggregation properties, such as lag-time and fibril stability.
    10/2014; 62(1). DOI:10.1002/jccs.201400272
  • Jinghui Wang · Ming Li · Dan Qi · Wei Shen · Rongxing He · Sheng Hsien Lin
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    ABSTRACT: An efficient strategy was provided by adopting different number of electron-deficient units (pyrimidyl and quinolyl) into parent coumarin sensitizers to obtain excellent absorption in short-wavelength region (B2 band), which eventually improves the performance of DSSCs. Density functional theory calculations were performed on both free dyes and dye/TiO2 complexes. As expected, introducing single electron-deficient unit results in a positive influence on power conversion efficiency (η) of DSSCs because of the larger short-circuit current density (Jsc is proportional to optical absorption (φLHE), charge separation, dye regeneration (φreg) and electron injection (φinject)) and the higher open circuit voltage (Voc). The introduction of more pyrimidine facilitates charge separation and favors effective electron injection, whereas the second quinoline displays opposite effect. The results give a guidance to design promising candidates for the future DSSCs applications.
    RSC Advances 10/2014; 4(96). DOI:10.1039/C4RA07904C · 3.84 Impact Factor
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    ABSTRACT: RATIONALE: Although several reaction models have been proposed in the literature to explain matrix-assisted laser desorption/ionization (MALDI), further study is still necessary to explore the important ionization pathways that occur under the high-temperature environment of MALDI. 2,4,6-Trihydroxyacetophenone (THAP) is an ideal compound for evaluating the contribution of thermal energy to an initial reaction with minimum side reactions. METHODS: Desorbed neutral THAP and ions were measured using a crossed-molecular beam machine and commercial MALDI-TOF instrument, respectively. A quantitative model incorporating an Arrhenius-type desorption rate derived from transition state theory was proposed. Reaction enthalpy was calculated using GAUSSIAN 03 software with dielectric effect. Additional evidence of thermal-induced proton disproportionation was given by the indirect ionization of THAP embedded in excess fullerene molecules excited by a 450 nm laser. RESULTS: The quantitative model predicted that proton disproportionation of THAP would be achieved by thermal energy converted from a commonly used single UV laser photon. The dielectric effect reduced the reaction Gibbs free energy considerably even when the dielectric constant was reduced under high-temperature MALDI conditions. With minimum fitting parameters, observations of pure THAP and THAP mixed with fullerene both agreed with predictions. CONCLUSIONS: Proton disproportionation of solid THAP was energetically favorable with a single UV laser photon. The quantitative model revealed an important initial ionization pathway induced by the abrupt heating of matrix crystals. In the matrix crystals, the dielectric effect reduced reaction Gibbs free energy under typical MALDI conditions. The result suggested that thermal energy plays an important role in the initial ionization reaction of THAP. Copyright (C) 2014 John Wiley & Sons, Ltd.
    Rapid Communications in Mass Spectrometry 08/2014; 28(15):1716-22. DOI:10.1002/rcm.6952 · 2.64 Impact Factor
  • Yibo Lei · Le Yu · Bo Zhou · Chaoyuan Zhu · Zhenyi Wen · Sheng Hsien Lin
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    ABSTRACT: The photoisomerization of cis- and trans-stilbene through conical intersections (CI) is mainly governed by four dihedral angles around central C = C double bonds. The two of them are C-C= C-C and H-C=C-H dihedral angles that are found to form mirror rotation coordinate, and the mirror plane appears at the two dihedral angles equal to zeros with which middle state is defined through partial optimization. There exist the first-type of Hula-Twist-CI enantiomers, the second-type of Hula-Twist-CI enantiomers, the first-type of one-bond-flip-CI enantiomers, and the second type of one-bond-flip-CI enantiomers as well as cis-enantiomers and trans-enantiomers with respect to this mirror plane. The complete active space self-consistent field method is employed to calculate minimum potential energy profile along the mirror rotation coordinate for each enantiomers, and it is found that the left-hand manifold and the right-hand manifold of potential energy surfaces can be energetically transferred via photoisomerization. Furthermore, two dimensional potential energy surfaces in terms of the branching plane g-h coordinates are constructed at vicinity of each conical intersection, and the landscapes of conical intersections show distinct feature, and in excited state four potential wells separated in different section of g-h plane related to different conical intersections which indicate different photoisomerization pathways.
    The Journal of Physical Chemistry A 06/2014; 118(39). DOI:10.1021/jp5020109 · 2.78 Impact Factor
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    ABSTRACT: We consider a system of two coupled particles fluctuating between two states, with different interparticle interaction potentials and particle friction coefficients. An external action drives the interstate transitions that induces reciprocating motion along the internal coordinate x (the interparticle distance). The system moves unidirectionally due to rectification of the internal motion by asymmetric friction fluctuations and thus operates as a dimeric motor that converts input energy into net movement. We focus on how the law of interaction between the particles affects the dimer transport and, in particular, the role of thermal noise in the motion inducing mechanism. It is argued that if the interaction potential behaves at large distances as x(α), depending on the value of the exponent α, the thermal noise plays a constructive (α > 2), neutral (α = 2), or destructive (α < 2) role. In the case of α = 1, corresponding piecewise linear potential profiles, an exact solution is obtained and discussed in detail.
    The Journal of Chemical Physics 06/2014; 140(21):214108. DOI:10.1063/1.4880416 · 3.12 Impact Factor
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    ABSTRACT: Controlling π-electrons with delocalized character is one of the fundamental issues in femtosecond and attosecond chemistry. Localization of π-electron rotation by using laser pulses is expected to play an essential role in nanoscience. The π-electron rotation created at a selected aromatic ring of a single molecule induces a local intense electromagnetic field, which is a new type of ultrafast optical control functioning. We propose a quantum localization of coherent π-electron angular momentum in (P)-2,2′-biphenol, which is a simple, covalently linked chiral aromatic ring chain molecule. The localization considered here consists of sequential two steps: the first step is to localize the π-electron angular momentum at a selected ring of the two benzene rings, and the other is to maintain the localization. Optimal control theory was used for obtaining the optimized electric fields of linearly polarized laser pulses to realize the localization. The optimal electric fields and the resultant coherent electronic dynamics are analyzed.
    Journal of Physical Chemistry Letters 05/2014; 5(11):2044–2049. DOI:10.1021/jz5007109 · 7.46 Impact Factor
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    ABSTRACT: We study analytically the effect of a small inertial correction on the properties of adiabatically driven flashing ratchets. Parrondo's lemma [J. M. R. Parrondo, Phys. Rev. E 57, 7297 (1998)] is generalized to include the inertial term so as to establish the symmetry conditions allowing directed motion (other than in the overdamped massless case) and to obtain a high-temperature expansion of the motion velocity for arbitrary potential profiles. The inertial correction is thus shown to enhance the ratchet effect at all temperatures for sawtooth potentials and at high temperatures for simple potentials described by the first two harmonics. With the special choice of potentials represented by at least the first three harmonics, the correction gives rise to the motion reversal in the high-temperature region. In the low-temperature region, inertia weakens the ratchet effect, with the exception of the on-off model, where diffusion is important. The directed motion adiabatically driven by potential sign fluctuations, though forbidden in the overdamped limit, becomes possible due to purely inertial effects in neither symmetric nor antisymmetric potentials, i.e., not for commonly used sawtooth and two-sinusoid profiles.
    Physical Review E 05/2014; 89(5-1):052131. DOI:10.1103/PhysRevE.89.052131 · 2.33 Impact Factor
  • Chih-Kai Lin · Michitoshi Hayashi · Sheng Hsien Lin
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    ABSTRACT: Sum-frequency generation (SFG) spectroscopy is a powerful tool for not only identifying molecular species but also analyzing orientation configurations on a surface/interface. In this Article, we presented reformulation of the theoretical framework of electronic SFG spectroscopy, the signal of which could be greatly enhanced by tuning one or two incident beam frequencies resonant with electronic excited states. Simulated electronic SFG spectra resonant at the sum frequency of a pair of coumarin-derivative pH-indicator surfactant molecules, 4-methyl-7-hydroxycoumarin and its anionic counterpart (MHC/MHC–), floating on the water surface were carried out as a demonstration.
    The Journal of Physical Chemistry C 11/2013; 117(45):23797–23805. DOI:10.1021/jp407881a · 4.77 Impact Factor
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    ABSTRACT: Multi-reference configuration interaction with single and double excitation method has been utilized to calculate the potential energy surfaces of the five low-lying electronic states (1)A1, (1)A2, (3)A2, (1)B2, and (3)B2 of carbon dioxide molecule. Topology of intersections among these five states has been fully analyzed and is associated with double-well potential energy structure for every electronic state. The analytical potential energy surfaces based on the reproducing kernel Hilbert space method have been utilized for illustrating topology of surface crossings. Double surface seam lines between (1)A1 and (3)B2 states have been found inside which the (3)B2 state is always lower in potential energy than the (1)A1 state, and thus it leads to an angle bias collision dynamics. Several conical∕surface intersections among these five low-lying states have been found to enrich dissociation pathways, and predissociation can even prefer bent-geometry channels. Especially, the dissociation of O((3)P) + CO can take place through the intersection between (3)B2 and (1)B2 states, and the intersection between (3)A2 and (1)B2 states.
    The Journal of Chemical Physics 10/2013; 139(15):154302. DOI:10.1063/1.4824483 · 3.12 Impact Factor
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    ABSTRACT: A series of dyes based on a porphyrin donor and a cyanoacrylic acid anchor/acceptor group for solar cell application are investigated with regards to varied-length π-spacers affecting the photo-to-electric conversion efficiency (PCE). Investigations are firstly performed on three porphyrin sensitizers with 1-3 conjugated phenylethynyl (PE) units, which have experimentally proved that the efficiency of power conversion decreases systematically with increasing spacer length. The distances and amounts of charge transfer after photoexcitation are calculated. In the PE bridged porphyrin dyes, the calculated electron injection driving forces and the regeneration driving forces gradually decrease as the distance of the π-spacer increases. Our theoretical calculations can reproduce well the experimental conclusion, showing that the photo-to-electric efficiency has a strong distance dependence for the electron-rich phenyl spacer. Then we replace the phenyl group with a pyrimidyl (PM) group to uncover how the characteristics of the π-spacer affect the performance of optical absorption, charge separation, and the regeneration process, to further improve the power conversion. We find that the adoption of electron-deficient pyrimidyl can break and even remove the distance dependence of the π-spacer. Some integral factors affecting the dye performance, such as short-circuit photocurrent, open-circuit voltage and charge collection efficiency are analyzed. It would help to interpret what role the electron deficient π-spacers with varied lengths will play and how they are expected to behave in the performance of sensitizers. In this regard, this study presents us with a promising way to design novel functional dyes and to utilize the potential advantages of the lengthy spacer dyes.
    RSC Advances 10/2013; 3(38):17515. DOI:10.1039/c3ra40702k · 3.84 Impact Factor
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    ABSTRACT: Ionization and dissociation of 2- and 3-methyl cyclopentanones have been investigated in molecular beams by their irradiation with intense 394 and 788 nm laser fields with pulse duration of 90 fs and intensity of 3 x 10(13)-4 x 10(14) W/cm(2). The analysis of the resulting mass spectra allowed us to discern the effects of methyl substitution and its position on the outcome of ionization/dissociation processes induced by the intense femtosecond laser field. Generalized Keldysh-Faisal-Reiss (g-KFR) and ab initio G3(MP2, CCSD)//B3LYP/6-31G*/RRKM theoretical calculations helped to uncover the formation mechanism of major ionic fragments observed in the mass spectra including C5H10+, C4H6O+, C3H3O+, C3H4O+, C3Hx+, and C2Hx+.
    Chemical Physics Letters 10/2013; 586:21-28. DOI:10.1016/j.cplett.2013.09.009 · 1.99 Impact Factor
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    ABSTRACT: The effect of substitutional Si, Fe, and Si and Fe (co)doping on the electronic structure and optical properties of anatase and rutile TiO2 have been investigated by the density functional theory. The calculated results indicate that Si doping TiO2 will induce an obvious band gap narrowing by mixing O 2p with Si 3p states, and a series of impurity energy levels (Fe 3d) appear in edge of the VB and the CB through Fe doping. The synergistic effects of Si and Fe codoping can extend optical absorption edge, which leads to higher visible-light photocatalytic activities than pure and monodoped anatase TiO2. Si and Fe-codoped TiO2 nanoparticles was prepared by a sol–gel-solvothermal method, and the photocatalytic activity of TiO2 nanoparticles was examined by measuring the rate of methylene blue decomposition. The experimental results show that Si and Fe-codoped TiO2 sample exhibits better optical absorption performance and higher photocatalytic activities for the degradation of methylene blue than pure and monodoped TiO2, which verifies the reliability of our calculated results.
    Applied Catalysis B Environmental 10/2013; s 142–143:38–44. DOI:10.1016/j.apcatb.2013.04.061 · 6.01 Impact Factor
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    ABSTRACT: We investigate a Brownian pump which, being powered by a flashing ratchet mechanism, produces net particle transport through a membrane. The extension of the Parrondo's approach developed for reversible Brownian motors [Parrondo, Phys. Rev. E 57, 7297 (1998)] to adiabatically driven pumps is given. We demonstrate that the pumping mechanism becomes especially efficient when the time variation of the potential occurs adiabatically fast or adiabatically slow, in perfect analogy with adiabatically driven Brownian motors which exhibit high efficiency [Rozenbaum et al., Phys. Rev. E 85, 041116 (2012)]. At the same time, the efficiency of the pumping mechanism is shown to be less than that of Brownian motors due to fluctuations of the number of particles in the membrane.
    Physical Review E 07/2013; 88(1-1):012104. DOI:10.1103/PhysRevE.88.012104 · 2.33 Impact Factor
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    ABSTRACT: Recently the quantum chemistry program can provide the anharmonic potentials for polyatomic molecules and clusters. It makes the quantum calculation of intramlecular vibrational redistribution (IVR) rates and intramolecular vibrational energy transfer possible. In the present paper, we apply the adiabatic approximation method to treat these two intramolecular energy redistribution processes. Using this method, we calculate the IVR rates of the dipeptides (glycyl tyrosine (GlyTyr) and leucyl tyrosine (LeuTyr)) and their cation radicals from the high frequency modes to the low frequency modes. Our theoretical results of the IVR lifetimes of the high frequency modes, like C-H, N-H, and O-H stretching modes, for both GlyTyr and LeuTyr molecules and their cation radicals are about 1 ps, 10 ps, and 100 ps, respectively. It provides theoretical support for the claim that IVR takes place prior to dissociation and the IVR rates are determined by the functional group rather than the degrees of freedom of the system. Thus the Rice-Ramsperger-Kassel-Marcus (RRKM) theory is suitable for investigating the photodissociation process of dipeptides. In addition, the calculated intramolecular energy transfer rate from O-H stretching mode of the C-termius of dipeptides to N-H mode of N-terminus is close to IVR rate.
    07/2013; 60(7). DOI:10.1002/jccs.201300214
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    ABSTRACT: The b-hairpin is a building block in the β-sheet structure. Understanding the formation of the β-hairpin may provide insight into the formation of β-sheet structures in, for example, protein amyloids. In this study, we performed molecular dynamics (MD) simulations to investigate the temperature-dependent transition behaviors of the GB1 β-hairpin peptide. The simulated results are analysed in terms of distances between pairs of peptide bonds and site-dependent dihedral angles. Our results show that the properties of the hairpin can be site-dependent and that the dependency is primarily associated with the hairpin's geometrical shape and specific interactions, such as hydrophobic clustering. Thus our study provides a foundation for the interpretation of probe-dependent experimental results.
    07/2013; 60(7). DOI:10.1002/jccs.201300173
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    ABSTRACT: The interactions between Ammoeng 100 and water are probed using high-pressure infrared measurements and DFT-calculations. The results of infrared absorption profiles suggest that the energetically favored approach for water molecules to interact with Ammoeng 100 is via the formation of anion-water interactions, whereas the alkyl C-H groups play much less important roles. After comparison with pure Ammoeng 100, it appears that no appreciable changes in band frequencies of alkyl C-H vibrations occurred as Ammoeng 100 was mixed with D2O. The presence of D2O has a red-shift effect on the peak frequency of the S[double bond, length as m-dash]O stretching vibration under the pressures below 1 GPa in comparison to the absorption frequencies of pure Ammoeng 100. This observation is likely related to local structures of the S[double bond, length as m-dash]O groups interacting with D2O molecules. DFT-calculations indicate that the most energetically favored conformation of ion pairs should be the species having only one hydrophilic hydrogen bonding. The results of calculations reveal that water addition may induce the partial replacement of C-HO interactions with strong hydrogen bonding between anions and water molecules.
    Physical Chemistry Chemical Physics 06/2013; DOI:10.1039/c3cp51396c · 4.20 Impact Factor

Publication Stats

1k Citations
381.45 Total Impact Points


  • 2008–2015
    • National Chiao Tung University
      • Department of Applied Chemistry
      Hsin-chu-hsien, Taiwan, Taiwan
  • 1994–2014
    • Academia Sinica
      • Institute of Atomic and Molecular Sciences
      T’ai-pei, Taipei, Taiwan
  • 2004–2008
    • National Dong Hwa University
      • Department of Chemistry
      Hualian, Taiwan, Taiwan
  • 2000–2008
    • National Taiwan University
      • • Department of Chemistry
      • • Center for Condensed Matter Sciences
      T’ai-pei, Taipei, Taiwan
  • 2006
    • National Academy of Sciences of Ukraine
      Kievo, Kyiv City, Ukraine