| 1. |
- Nilsson, Fritjof, 1978-
(författare)
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Meso-scale modelling of composites and semi-crystalline polymers
- 2009
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis covers the first few steps of a multi-scale computer simulation strategy for predicting physical properties of complex polymers like composites and semi-crystalline polymers. Meso-scale simulations of crystallization and solvent diffusion in polyethylene as well as simulations examining the geometrical impact on the effective permittivity of composites have been performed. These meso-scale models will in the near future be coupled to molecular dynamics models for increased realism and accuracy. The first paper was focused on solvent diffusion in spherulitic semi-crystalline polyethylene. Geometrical models of polyethylene spherulites were constructed and Monte-Carlo random walker simulations were used to estimate the geometrical impedance factor as function of volume crystallinity, mean free path and other geometry properties. Novel numerical off-lattice algorithms made it possible to increase the maximum volume crystallinity from 40 to 55%, to decrease the computation time a factor 100 and to use shorter and more realistic diffusion jump-lengths. The simulation results were in good agreement with experimental results and new analytical formulas were found that could be neatly fitted to both simulation data and experimental data. It was noticed that the geometrical impedance factor was proportional to the polymers mean free path length rather than its length/width aspect ratio and that the traditional Fricke formula for oblate spheroids was not able to correctly predict the diffusion behaviour in complex geometries like spherulites at medium-high volume crystal fractions. The second paper was focused on the electrostatics of composites. Geometrical models of layered composites were first obtained and the finite element method was then used to calculate the effective composite permittivity as function of particle content, particle shape, degree of mixing and other geometrical issues. Analytical lamellae formulas for 2- and 3-phase composites were formulated with clearly better correlation to corresponding finite element data than all other previously known analytical formulas. The analytical 3-phase formula was successfully compared with experimental data for mica/polyimide and it was noted that the influence of water and air was significant.
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| 2. |
- Zakomirnyi, Vadim, 1989-
(författare)
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Multicomponent Resonant Nanostructures: Plasmonic and Photothermal Effects
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In recent decades, plasmonic nanoparticles have attracted considerable attention due to their ability to localize electromagnetic energy at a scale much smaller than the wavelength of optical radiation. The study of optical plasmon waveguides (OPWs) in the form of chains of nanoparticles is important for modern photonics. However, the widespread use of OPWs is limited due to the suppression of the resonance properties of classical plasmon materials under laser irradiation. The study of the influence of nanoparticle heating on the optical properties of waveguides and the search for new materials capable of stable functioning at high temperatures is an important task.In this thesis, the processes occurring during heating of plasmon nanoparticles and OPWs are studied. For this purpose, a model was developed that takes into account the heat transfer between the particles of an OPW and the environment. The calculations used temperature-dependent optical constants. As one of possible ways to avoid thermal destabilization of plasmon resonanses, new materials for OPWs formed by nanoparticles were proposed. I show that titanium nitride is a promising thermally stable material, that might be useful for manufacturing of OPWs and that works in high intensity laser radiation.Another hot topic at present is the study of periodic structures of resonant nanoparticles. Periodic arrays of nanoparticles have a unique feature: the manifestation of collective modes, which are formed due to the hybridization of a localized surface plasmon resonance or a Mie resonance and the Rayleigh lattice anomaly. Such a pronounced hybridization leads to the appearance of narrow surface lattice resonances, the quality factor of which is hundreds of times higher than the quality factor of the localized surface plasmon resonance alone. Structures that can support not only electric, but also magnetic dipole resonances becomes extremely important for modern photonics on chip systems. An example of a material of such particles is silicon. Using the method of generalized coupled dipoles, I studied the optical response of arrays of silicon nanoparticles. It is shown that under certain conditions, selective hybridization of only one of the dipole moments with the Rayleigh anomaly occurs.To analyze optical properties of intermediate sized particles with N = 103-105 atoms and diameter of particle d < 12 nm an atomistic approach, where the polarizabilities can be obtained from the atoms of the particle, could fill an important gap in the description of nanoparticle plasmons between the quantum and classical extremes. For this purpose I introduced an extended discrete interaction model where every atom makes a difference in the formation optical properties of nanoparticles within this size range. In this range are first principal approaches not applicable due to the high number of atoms and classical models based on bulk material dielectric constants are not available due to high influence from quantum size effects and corrections to the dielectric constant. To parametrize this semi-empirical model I proposed a method based on the concept of plasmon length. To evaluate the accuracy of the model, I performed calculations of optical properties of nanoparticles with different shapes: regular nanospheres, nanocubes and nanorods. Subsequently, the model was used to calculate hollow nanoparticles (nano-bubbles).
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| 3. |
- Harczuk, Ignat, 1987-
(författare)
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Atomic decomposition of molecular properties
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis, new methodology of computing properties aimed for multipleapplications is developed. We use quantum mechanics to compute propertiesof molecules, and having these properties as a basis, we set up equations basedon a classical reasoning. These approximations are shown to be quite good inmany cases, and makes it possible to calculate linear and non-linear propertiesof large systems.The calculated molecular properties are decomposed into atomic propertiesusing the LoProp algorithm, which is a method only dependent on the overlapmatrix. This enables the expression of the molecular properties in the two-site atomic basis, giving atomic, and bond-centric force-fields in terms of themolecular multi-pole moments and polarizabilities. Since the original LoProptransformation was formulated for static fields, theory is developed which makesit possible to extract the frequency-dependent atomic properties as well. Fromthe second-order perturbation of the electron density with respect to an externalfield, LoProp is formulated to encompass the first order hyperpolarizability.The original Applequist formulation is extended into a quadratic formula-tion, which produces the second-order shift in the induced dipole moments of thepoint-dipoles from the hyperpolarizability. This enables the calculation of a to-tal hyperpolarizability in systems consisting of interacting atoms and molecules.The first polarizability α and the first hyperpolarizability β obtained via theLoProp transformation are used to calculate this response with respect to anexternal field using the quadratic Applequist equations.In the last part, the implemented analytical response LoProp procedureand the quadratic Applequist formalism is applied to various model systems.The polarizable force-field that is obtained from the decomposition of the staticmolecular polarizability α is tested by studying the one-photon absorption spec-trum of the green fluorescent protein. From the frequency dispersion of thepolarizability α(ω), the effect of field perturbations is evaluated in classicaland QM/MM applications. Using the dynamical polarizabilities, the Rayleigh-scattering of aerosol clusters consisting of water and cis–pinonic acid moleculesis studied. The LoProp hyperpolarizability in combination with the quadraticApplequist equations is used to test the validity of the model on sample wa-ter clusters of varying sizes. Using the modified point-dipole model developedby Thole, the hyper-Rayleigh scattering intensity of a model collagen triple-helix is calculated. The atomic dispersion coefficients are calculated from thedecomposition of the real molecular polarizability at imaginary frequencies. Fi-nally, using LoProp and a capping procedure we demonstrate how the QM/MMmethodology can be used to compute x-ray photoelectron spectra of a polymer.
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| 4. |
- Makris, Georgios, 1977-
(författare)
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Suicide Seasonality : Theoretical and Clinical Implications
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Background: Although suicide seasonality has been well-documented, surprisingly little is known about its underlying mechanisms.Methods: In this thesis, data from three Swedish registers (Cause of Death Register, National Patient Register, Prescribed Drugs Register) and data from the Swedish Meteorological and Hydrological Institute were used.In Study I, the amplitude of suicide seasonality was estimated in completed suicides in 1992-2003 in individuals with different antidepressant medications or without antidepressants.In Study II, monthly suicide and sunshine data from 1992-2003 were used to examine the association between suicide and sunshine in groups with and without antidepressants.In Study III, the relationship between season of initiation of antidepressant treatment and the risk of suicidal behavior was explored in patients with a new treatment episode with antidepressant medication.In Study IV, the complex association between sunshine, temperature and suicidal behavior was investigated in patients with a new treatment episode with an antidepressant in two exposure windows (1-4 and 5-8 weeks) before the event.Findings: Study I: Higher suicide seasonality was found in individuals treated with selective serotonin reuptake inhibitors (SSRIs) compared with those given a different antidepressant treatment or those without any antidepressant treatment.Study II: In individuals treated with SSRIs, there was a positive association between sunshine and suicide, with the association stronger in men treated with SSRIs compared with men treated with other antidepressants. An effect modification by age was observed.Study III: The elderly (65+) had a higher risk of suicide when initiating antidepressant treatment in summer and a higher risk of suicide attempt when starting antidepressant therapy in spring and summer. Younger patients (0-24) demonstrated a higher risk of suicide attempt when treatment was initiated in autumn.Study IV: In the elderly (65+), a harmful association was observed between the risk of suicide attempt and the average daily temperature during the four weeks before the suicide attempt, as well as with average daily sunshine during both exposure windows (1-4 and 5-8 weeks) before the suicide attempt.Significance: Our results provide epidemiological support for the role of the serotonergic system in seasonality of suicide in which both medication and climate may be involved.
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| 5. |
- Michelgård Palmquist, Åsa, 1973-
(författare)
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Positron Emission Tomography (PET) Studies in Anxiety Disorders
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Anxiety disorders are very common and the primary feature is abnormal or inappropriate anxiety. Fear and anxiety is often mediated by the amygdala, a brain structure rich in substance P (SP) and neurokinin 1 (NK1) receptors. To learn more about how the human amygdala is modulated by fear and anxiety in event-triggered anxiety disorders and to investigate if the SP/NK1 receptor system is affected, regional cerebral blood flow (rCBF) ([15O]-water; Study I and II) and the SP/NK1 receptor system ([11C]GR205171; Study III and IV) were studied with positron emission tomography (PET). In Study I we investigated the neural correlates of affective startle modulation in persons with specific phobia by measuring rCBF during exposure to fearful and non-fearful pictures, paired and unpaired with acoustic startle stimuli. Fear-potentiated startle was associated with activation of the affective part of the anterior cingulate cortex and the left amygdaloid–hippocampal area. In Study II short-term drug treatment effects on rCBF in patients diagnosed with social phobia was evaluated, comparing the NK1 receptor antagonist GR205171 to the selective serotonin reuptake inhibitor citalopram and placebo. Social anxiety and neural activity in the medial temporal lobe including the amygdala was significantly reduced by both drugs but not placebo. In Study III we investigated if activity in the SP/NK1 receptor system in the amygdala would be affected by fear provocation in individuals with specific snake or spider phobia. Fear provocation was associated with a decreased uptake of the NK1 antagonist [11C]GR205171 in the amygdala, possibly explained by an increase in endogenous SP release occupying the NK1 receptors. Study IV was conducted to explore the resting state NK1 receptor availability in PTSD patients as compared to healthy controls. Increased resting state binding of the tracer [11C]GR205171 in the amygdala of patients with PTSD suggested an increased amount of available receptors. In summary, fear and fear-potentiated startle modulates the human amygdala, possibly through the SP/NK1 receptor system.
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| 6. |
- Frecus, Bogdan
(författare)
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Theoretical studies of EPR parameters of spin-labels incomplex environments
- 2013
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis encloses quantum chemical calculations performed in the framework of density functional response theory for evaluating electron paramagnetic resonance (EPR) spin Hamiltonian parameters of various spin-labels in different environments. These parameters are the well known electronic g-tensor and the nitrogen hyperfine coupling constants, which are extensively explored in this work for various systems. A special attention was devoted to the relationships that form between the structural and spectroscopic properties that can be accounted for as an environmental inuence. Such environmental effects were addressed either within a fully quantum mechanical formalism, involving simplified model structures that still capture the physical properties of the extended system, or by employing a quantum mechanics/molecular mechanics (QM/MM) approach. The latter implies that the nitroxide spin label is treated quantum mechanically, while the environment is treated in a classical discrete manner, with appropriate force fields employed for its description. The state-of- the art techniques employed in this work allow for an optimum accounting of the environmental effects that play an important role for the behaviour of EPR properties of nitroxides spin labels. One achievement presented in this thesis includes the first theoretical con_rmation of an empirical assumption that is usually made for inter-molecular distance measurement experiments in deoxyribonucleic acid (DNA), involving pulsed electron-electron double resonance (PELDOR) and site-directed spin labeling (SDSL) techniques. This refers to the fact that the EPR parameters of the spin-labels are not affected by their interaction with the nucleobases from which DNA is constituted. Another important result presented deals with the inuence of a supramolecular complex on the EPR properties of an encapsulated nitroxide spin-label. The enclusion complex affects the hydrogen bonding topology that forms around the R2NO moiety of the nitroxide. This, on the other hand has a major impact on its structure which further on governs the magnitude of the spectroscopic properties. The projects and results presented in this thesis offer an example of successful usage of modern quantum chemistry techniques for the investigation of EPR parameters of spin-labels in complex systems.
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| 7. |
- Hammar, Peter, 1980-
(författare)
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Quantum Chemical Studies of Mechanisms and Stereoselectivities of Organocatalytic Reactions
- 2009
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- As the field of organocatalysis is growing, it is becoming more important to understand the specific modes of action of these new organic catalysts. Quantum chemistry, in particular density functional theory, has proven very powerful in exploring reaction mechanisms as well as selectivities in organocatalytic reactions, and is the tool used in this thesis. Different reaction mechanisms of several organocatalytic reactions have been examined, and we have been able to exclude various reaction pathways based on the calculated reaction barriers. The origins of stereoselection in a number of reactions have been rationalized. The computational method has generally reproduced the experimental stereoselectivities satisfactorily. The amino acid-catalyzed aldol reaction has previously been established to go through an enamine intermediate. In the first study of this thesis the understanding of this kind of reactions has been expanded to the dipeptide-catalyzed aldol reaction. The factors governing the enantioselection have been studied, showing how the chirality of the amino acids controls the conformation of the transition state, thereby determining the configuration of the product. In the cinchona thiourea-catalyzed Henry reaction two reaction modes regarding substrate binding to the two sites of the catalyst have been investigated, showing the optimal arrangement for this reaction. This enabled the rationalization of the observed stereoselectivity. The hydrophosphination of α,β-unsaturated aldehydes was studied. The bulky substituent of the chiral prolinol-derived catalyst was shown to effectively shield one face of the reactive iminium intermediate, thereby inducing the stereoselectivity. The transfer hydrogenation of imines using Hantzsch esters as hydride source and axially chiral phosphoric acid catalyst has also been explored. A reaction mode where both the Hantzsch ester and the protonated imine are hydrogen bonded to the phosphoric acid is demonstrated to be the preferred mode of action. The different arrangements leading to the two enantiomers of the product are evaluated for several cases, including the hydride transfer step in the reductive amination of α-branched aldehydes via dynamic kinetic resolution. Finally, the intramolecular aldol reaction of ketoaldehydes catalyzed by guanidinebased triazabicyclodecene (TBD) has been studied. Different mechanistic proposals have been assessed computationally, showing that the favoured reaction pathway is catalyzed by proton shuttling. The ability of a range of guanidines to catalyze this reaction has been investigated. The calculated reaction barriers reproduced the experimental reactivities quite well.
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| 8. |
- Jamshidi Zavaraki, Asghar, 1984-
(författare)
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Engineering Multicomponent Nanostructures for MOSFET, Photonic Detector and Hybrid Solar Cell Applications
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Silicon technologyhas been seekingfor a monolithic solution for a chip where data processing and data communication is performed in the CMOS part and the photonic component, respectively. Traditionally, silicon has been widely considered for electronic applications but not for photonic applications due to its indirect bandgap nature. However, band structure engineering and manipulation through alloying Si with Ge and Sn has opened new possibilities. Theoretical calculations show that it is possible to achieve direct transitions from Ge ifit is alloyed with Sn. Therefore, a GeSn system is a choice to get a direct bandgap. Extending to ternary GeSnSi and quaternary GeSnSiCstructures grown on Si wafers not only makes the bandgap engineering possible but also allowsgrowing lattice matched systems with different strain and bandgaps located in the infrared region. Different heterostructures can be designed and fabricated for detecting lightas photonic sensing oremitting the light as lasers. Alloying not only makes engineering possible but it also induces strain which plays an important role for electronic applications. Theoretical and experimental works show that tensile strain could increase the mobility, which is promising for electronic devices where high mobility channels for high performance MOSFETs is needed to speed up the switching rate. On the other hand, high n-doping in tensile strains in p-i-n structures makesΓ band transitions most probable which is promising for detection and emission of the light. As another benefit of tensile strain, the direct bandgap part shrinks faster than the indirect one if the strain amount is increased.To get both electronic and photonic applications of GeSn-based structures, two heterostructures (Ge/GeSn(Si)/GeSi/Ge/Si and Ge/GeSn/Si systems), including relaxed and compressive strained layers used to produce tensile strained layers, were designed in this thesis. The low temperature growth is of key importance in this work because the synthesis of GeSn-based hetrostructures on Si wafers requires low thermal conditions due tothe large lattice mismatch which makes them metastable. RPCVD was used to synthesize theseheterostructures because not only it offers a low temperature growth but also because it is compatible with CMOS technology. For utilization of these structures in devices, n-type and p-type doping of relaxed and compressive strained layers were developed. HRRLMs, HRTEM, RBS, SIMS, and FPP techniques were employed to evaluatestrain, quality, Sn content and composition profile of the heterostructures.The application of GeSn-based heterostructures is not restricted to electronics and photonics. Another application investigated in this work is photovoltaics. In competition with Si-based solar cells, which have, or areexpected to have,high stability and efficiency, thirdgeneration solar cells offer the use of low cost materials and production and can therefore be an alternative for future light energy conversion technology. Particularly, quantum dot sensitized solar cells are associated with favorable properties such as high extrinsic coefficients, size dependent bandgaps and multiple exciton generation and with a theoretical efficiencyof 44%. In this work, two categories of QDs, Cd-free and Cd-based QDs were employed as sensitizers in quantum dot sensitized solar cells (QDSSCs). Cd-based QDs have attracted large interest due to high quantum yield,however, toxicityremains still totheir disadvantage. Mn doping as a bandgap engineering tool for Cd-based type IIZnSe/CdS QDs wasemployed to boostthe solar cell efficiency. Theoretical and experimental investigations show that compared to single coreQDSSCs,typeII core-shells offer higher electron-hole separation due to efficient band alignment where the photogenerated electrons and holes are located in the conduction band of the shell and valence band of the core, respectively. This electron-hole separation suppresses recombination and by carefully designing the band alignment in the deviceit can increase the electron injection and consequently the power conversion efficiency of the device.Considering eco-friendly and commercialization aspects, three different “green” colloidal nanostructures having special band alignments, which are compatible for sensitized solar cells, were designed and fabricated by the hot injection method. Cu2GeS3-InP QDs not only can harvest light energy up to the infraredregion but can also be usedastypeII QDs. ZnS-coating was employed as a strategy to passivate the surface of InP QDs from interaction with air and electrolyte. In addition, ZnS-coating and hybrid passivation was applied for CuInS2QDs to eliminate surface traps.
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| 9. |
- Li, Xin
(författare)
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Applications of Molecular Dynamics in Atmospheric and Solution Chemistry
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis focuses on the applications of molecular dynamics simulation techniques in the fields of solution chemistry and atmospheric chemistry. The work behind the thesis takes account of the fast development of computer hardware, which has made computationally intensive simulations become more and more popular in disciplines like pharmacy, biology and materials science. In molecular dynamics simulations using classical force fields, the atoms are represented by mass points with partial charges and the inter-atomic interactions are modeled by approximate potential functions that produce satisfactory results at an economical computational cost. The three-dimensional trajectory of a many-body system is generated by integrating Newton’s equations of motion, and subsequent statistical analysis on the trajectories provides microscopic insight into the physical properties of the system. The applications in this thesis of molecular dynamics simulations in solution chemistry comprise four aspects: the 113Cd nuclear magnetic resonance shielding constant of aqua Cd(II) ions, paramagnetic 19F nuclear magnetic resonance shift in fluorinated cysteine, solvation free energies and structures of metal ions, and protein adsorption onto TiO2. In the studies of nuclear magnetic resonance parameters, the relativistic effect of the 113Cd nucleus and the paramagnetic shift of 19F induced by triplet O2 are well reproduced by a combined molecular dynamics and density functional theory approach. The simulation of the aqua Cd(II) ion is also extended to several other monovalent, divalent and trivalent metal ions, where careful parameterization of the metal ions ensures the reproduction of experimental solvation structures and free energies. Molecular dynamics simulations also provided insight into the mechanism of protein adsorption onto the TiO2 surface by suggesting that the interfacial water molecules play an important role of mediating the adsorption and that the hydroxylated TiO2 surface has a large affinity to the proteins. The applications of molecular dynamics simulations in atmospheric chemistry are mainly focused on two types of organic components in aerosol droplets: humic-like compounds and amino acids. The humic-like substances, including cis-pinonic acid, pinic acid and pinonaldehyde, are surface-active organic compounds that are able to depress the surface tension of water droplets, as revealed by both experimental measurements and theoretical computations. These compounds either concentrate on the droplet surface or aggregate inside the droplet. Their effects on the surface tension can be modeled by the Langmuir-Szyszkowski equation. The amino acids are not strong surfactants and their influence on the surface tension is much smaller. Simulations show that the zwitterionic forms of serine, glycine and alanine have hydrophilic characteristics, while those of valine, methionine and phenylalanine are hydrophobic. The curvature dependence of the surface tension is also analyzed, and a slight improvement in the Köhler equation is obtained by introducing surface tension corrections for droplets containing glycine and serine. Through several examples it is shown that molecular dynamics simulations serve as a promising tool in the study of aqueous systems. Both solute-solvent interactions and interfaces can be treated properly by choosing suitable potential functions and parameters. Specifically, molecular dynamics simulations provide a microscopic picture that evolves with time, making it possible to follow the dynamic processes such as protein adsorption or atmospheric droplet formation. Moreover, molecular dynamics simulations treat a large number of molecules and give a statistical description of the system; therefore it is convenient to compare the simulated results with experimentally measured data. The simulations can provide hints for better design of experiments, while experimental data can be fed into the refinement of the simulation model. As an important complementary to experiments, molecular dynamics simulations will continue to play significant roles in the research fields of physics, chemistry, materials science, biology and medicine.
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| 10. |
- Liu, Qingyun
(författare)
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Studies of optical properties of lanthanide upconversion nanoparticles for emerging applications.
- 2020
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- YTTERBY, a small village very close to Stockholm where I live, is the place in the world which has lent its name to the largest number of elements in the periodic table, namely four - YTTRIUM, YTTERBIUM, ERBIUM and TERBIUM. Three more lanthanide elements were discovered from the now empty quarry located in this village. By the time of their discoveries in the 19th century little could be known about their fantastic properties, the versatility of their use and functionality in what we now call nanotechnology. This is a circumstance that motivated me to rather recently enter lanthanide research, in particular studies of their outstanding optical properties for the purpose of information technology and energy harvesting.So far, upconversion nanoparticles (UCNPs) have been much explored as unique spectral converters for various applications, like biotechnology, information technology and photovoltaic devices due to properties like sharp emission profiles, low autofluorescence and large anti-Stoke shifts. Still, there is much to explore and to understand in order to fully utilize the very unique properties of UCNPs. The kinetic dynamics of the upconversion process is one such aspect that is not well understood, and a deeper understanding of the kinetic dynamics of lanthanide upconversion systems could thus broaden their applications. Therefore, the work of this thesis is focused on investigating the kinetic dynamics of upconversion processes mainly based on systems with NaYF4 as host material, and Yb3+/Er3+ or Yb3+/Tm3+ embedded as sensitizer/activator. Through rate equation models, the kinetic dynamics of upconversion are comparatively investigated with numerical simulations and analytical derivation. The temporal response regarding upconverted luminescence and quantum yield power density dependence, excitation duration response and excitation frequency response of the upconversion systems are investigated and the corresponding applications for multicolor imaging, optical encoding, photovoltaics, IR photodetectors are explored and analyzed in the thesis, taking advantage of the kinetic properties.
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