In order to explore the quantum-to-classical transition, the ambition of this thesis was the design and synthesis of tailor-made molecules for matter-wave interference experiments. Firstly, the focus was set on a deeper understanding of the influence of a molecule’s internal structure, especially its polarizability, on quantum interference. Furthermore, the limits of quantum mechanics were addressed by increasing the size of the interfering objects. The metrological aspect of molecule interferometry - to measure influences of molecule properties on the wave nature - is described in the first part of this thesis. Two fourfold perfluorohexyl functionalized constitutional isomers were synthesized in order to demonstrate that different molecular conformations can be distinguished in quantum interference experiments. A tetrahedral isomer and a rod-like oligo(phenylene ethynylene) derivative were applied in a near-field Kapitza-Dirac-Talbot-Lau interferometer. Although de Broglie quantum interference describes the center of mass motion of a massive body, it was shown to be sensitive to the internal molecular structure of the constitutional isomers. The different total susceptibilities of both isomers lead to different de Broglie interference shifts in the presence of external electric fields. The isomers thus become distinguishable in spite of their identical mass and chemical sum formula. Besides metrological applications, a main goal of this thesis was to synthesize model compounds for molecule interferometry to increase the preexisting mass record for quantum interferometry, which was held by the fluorofullerene C60F48 with a molecular weight of 1 633 g/mol. Near-field interferometry is a promising concept to set new records and thus to approach the quantum-to-classical transition. To meet the requirements of quantum studies with complex organic molecules in a Kapitza-Dirac-Talbot-Lau near-field interferometer – high volatility, high stability, and high molecular mass – we chose the functionalization of tetraarylporphyrins with perfluoroalkyl moieties. A modular synthesis of seven perfluoroalkyl-substituted porphyrin derivatives with up to 16 fluorous alkyl chains was presented. With this series in hand, it was possible to observe interference patterns for three of the seven derivatives. The heaviest molecule of this series for which the wave nature has been observed has a 3.3 fold higher molecular weight than the preexisting mass record for quantum interference. These experiments open a new window for quantum experiments with nanoobjects in a complexity class comparable to that of small proteins. The experimental setup of the near-field Kapitza-Dirac-Talbot-Lau interferometer is not restricted to monodisperse and pure starting compounds. It also allows for experiments with compound mixtures because individual components of compound libraries can be detected in the mass spectrometric detection unit. The preparation of porphyrin libraries gave access to compounds in a new mass region (> 10 000 g/mol). Preliminary investigations in near-field interferometers with these structures revealed suitable molecule beam properties. With these porphyrin libraries in hand, it is expected to exceed for the first time the ceiling of 10 000 g/mol for an interfering object in the future. Large, stable, highly volatile and fluorescent molecules were the goal of synthetic work that was performed for novel far-field interference experiments in a setup based on fluorescence detection. For this purpose three fluorescent fluorous phthalocyanine derivatives were prepared. With the help of a new laser-controlled micro-evaporation source it was possible to produce a beam of molecules with the required intensity and coherence. The observation of the wave nature of a free base phthalocyanine having a molecular weight of 1 299 g/mol set a new mass record for far-field molecule interferometry. The preexisting record for far-field interferometry was held by the fullerene C70 with a mass of 841 g/mol. To conclude, major contributions to the exploration of the frontiers of quantum mechanics were achieved by matter-wave interferometry using the perfluoroalkyl-functionalized molecules described in this thesis. \n
In order to explore the quantum-to-classical transition, the ambition of this thesis was the design and synthesis of tailor-made molecules for matter-wave interference experiments. Firstly, the focus was set on a deeper understanding of the influence of a molecule’s internal structure, especially its polarizability, on quantum interference. Furthermore, the limits of quantum mechanics were addressed by increasing the size of the interfering objects. The metrological aspect of molecule interferometry - to measure influences of molecule properties on the wave nature - is described in the first part of this thesis. Two fourfold perfluorohexyl functionalized constitutional isomers were synthesized in order to demonstrate that different molecular conformations can be distinguished in quantum interference experiments. A tetrahedral isomer and a rod-like oligo(phenylene ethynylene) derivative were applied in a near-field Kapitza-Dirac-Talbot-Lau interferometer. Although de Broglie quantum interference describes the center of mass motion of a massive body, it was shown to be sensitive to the internal molecular structure of the constitutional isomers. The different total susceptibilities of both isomers lead to different de Broglie interference shifts in the presence of external electric fields. The isomers thus become distinguishable in spite of their identical mass and chemical sum formula. Besides metrological applications, a main goal of this thesis was to synthesize model compounds for molecule interferometry to increase the preexisting mass record for quantum interferometry, which was held by the fluorofullerene C60F48 with a molecular weight of 1 633 g/mol. Near-field interferometry is a promising concept to set new records and thus to approach the quantum-to-classical transition. To meet the requirements of quantum studies with complex organic molecules in a Kapitza-Dirac-Talbot-Lau near-field interferometer – high volatility, high stability, and high molecular mass – we chose the functionalization of tetraarylporphyrins with perfluoroalkyl moieties. A modular synthesis of seven perfluoroalkyl-substituted porphyrin derivatives with up to 16 fluorous alkyl chains was presented. With this series in hand, it was possible to observe interference patterns for three of the seven derivatives. The heaviest molecule of this series for which the wave nature has been observed has a 3.3 fold higher molecular weight than the preexisting mass record for quantum interference. These experiments open a new window for quantum experiments with nanoobjects in a complexity class comparable to that of small proteins. The experimental setup of the near-field Kapitza-Dirac-Talbot-Lau interferometer is not restricted to monodisperse and pure starting compounds. It also allows for experiments with compound mixtures because individual components of compound libraries can be detected in the mass spectrometric detection unit. The preparation of porphyrin libraries gave access to compounds in a new mass region (> 10 000 g/mol). Preliminary investigations in near-field interferometers with these structures revealed suitable molecule beam properties. With these porphyrin libraries in hand, it is expected to exceed for the first time the ceiling of 10 000 g/mol for an interfering object in the future. Large, stable, highly volatile and fluorescent molecules were the goal of synthetic work that was performed for novel far-field interference experiments in a setup based on fluorescence detection. For this purpose three fluorescent fluorous phthalocyanine derivatives were prepared. With the help of a new laser-controlled micro-evaporation source it was possible to produce a beam of molecules with the required intensity and coherence. The observation of the wave nature of a free base phthalocyanine having a molecular weight of 1 299 g/mol set a new mass record for far-field molecule interferometry. The preexisting record for far-field interferometry was held by the fullerene C70 with a mass of 841 g/mol. To conclude, major contributions to the exploration of the frontiers of quantum mechanics were achieved by matter-wave interferometry using the perfluoroalkyl-functionalized molecules described in this thesis. \n
Matter-wave dualism is a fundamental concept in quantum physics. The observation of wave properties of heavy organic molecules can be used to approach the borderline between classical and quantum physics. Up to which mass and size do particles or molecules still have wave properties? This question is subject to be answered within this thesis and as part of the international nanoquestfit-project where many researchers of different disciplines are involved. \nThis thesis is a summary of the work done within a research collaboration between the group of Prof. Dr. Marcel Mayor (University of Basel) and the group of Prof. Dr. Markus Arndt (University of Vienna). The work is mainly focused on the development of novel quantum interference experiments that imply the development of new synthetic strategies towards tailor-made molecules. Novel interferometers have been developed by the Arndt group and therefore the molecular requirements changed strongly within the past years. The syntheses of these tailor-made molecules were performed by the author in the laboratories of Prof. Mayor in Basel. Quantum interference experiments and the preliminary investigations described within this work, namely the thermal stability test, the desorption studies and the laser-induced acoustic desorption have been performed by the Arndt group in Vienna. \nInvestigations at the interface of quantum and classical physics are a fascinating part of the research. The final goal is to approach the quantum-to-classical transition by the observation of quantum properties of large and complex molecules. In order to study the wave nature of such particles—a purely quantum mechanical phenomenon—synthetic procedures towards tailor-made compounds are developed to improve the observation of this phenomenon through matter-wave experiments. \nAt the starting point of this work, a series of highly fluorinated porphyrin-monomers set a new benchmark in high-mass quantum interference experiments. The highest masses of particles used in quantum interference experiments were around 10’000 g/mol. Thus, our objective was to reach masses up to 25’000 g/mol with the suitable features for the quantum interferometry experiments. \nIn the first chapter of this thesis, the principle of interferometry, the development and evolution of this technology are presented. In the subsequent chapters, the different synthetic approaches of the tailor-made molecules designed to improve the measurements and achieve the goal of this thesis are described. \nThe main part of this thesis is focused on the synthesis of tailor-made molecules for quantum interference experiments. In a first part, the synthesis of a novel, more massive fluorinated phthalocyanine is presented. That phthalocyanine was used in far-field quantum interference experiments. Unfortunately, the molecular requirements could not been tuned to observe wave-particle duality in these experiments. The second part focuses on the synthesis of three different molecular libraries. Molecular libraries are mixtures of molecules having the same core but a to some extent random number of long perfluorinated chains. The individual members within the library were observable in MALDI-TOF mass spectrometry. We attached the chains to three different cores to obtain three different molecular libraries. To produce a first generation of libraries we used diacetylene bond porphyrin-dimer. The rather limited reaction scope of diacetylene bond porphyrins was enhanced by the second generation of tetramers and pentamers. To compare the modularity of the synthesis of oligo-porphyrin systems two additional cores, a porphyrin-dimer and a porphyrin-trimer, have also been synthesized. The possibility to produce a molecular beam with the three molecular-libraries has been investigated by thermal studies, desorption experiments and laser-induced acoustic desorption. \nThe last part of the thesis is focused on the synthesis of photocleavable tags that can be attached to model compounds. These tags are synthesized since novel quantum interference experiments are based on light gratings where a mass difference is supposed to be observed at the detector level upon cleavage. The final idea is, in the near future, to attach these molecules to large particles, such as metal-nanoparticles, clusters or proteins. It is expected to enable the detection of mass differences of the intact clusters and the clusters with the cleaved tags. Three different model compounds have been synthesized. The cleavage of the tags was proven in solution upon irradiation of UV-light in solution, where a constant and reproducible decay was observed. In future quantum interference experiments, the cleavage should be performed in gas-phase as a final prove of concept. The molecules are currently under investigations in the Arndt group.
Abstract The synthesis and characterization of seven tailor‐made highly fluorous porphyrin derivatives are described, as large perfluoroalkyl‐functionalized organic molecules are the most complex objects for which the quantum wave nature has been observed so far. We have found, in particular, that tetrakis(pentafluorophenyl)porphyrin is a suitable starting point for a modular synthesis that is geared towards porphyrin derivatives with many peripheral fluorous chains. This allows us to tailor and optimize the sublimation features of these compounds for molecule interferometry. We have analyzed the evaporation process of one member of the series by determining the enthalpy of evaporation, as the creation of a sufficiently intense, slow molecular beam is crucial for quantum interference experiments. We present the quantum fringe pattern of a second member of the series, which we could obtain in a Kapitza–Dirac–Talbot–Lau interferometer.
We discuss new de Broglie coherence experiments in a near-field molecule interferometer with a variety of large organic molecules. While de Broglie coherence is to first order only associated with the center-of-mass motion of the diffracted particle, we here investigate the question as to which extent the internal molecular property is relevant for, compatible with or detrimental for maintaining coherence in the translational degree of freedom. External perturbations, such as inhomogeneous external electric fields, may influence the delocalized molecules inside the matter wave interferometer and they allow us to access the molecular polarizabilities, permanent or even fluctuating electric dipole moments. We extract information about the molecular states from the interference phase shifts as well as from the observed dephasing in a Kapitza-Dirac Talbot-Lau-Stark-deflectometer. We discuss the relevance of our experiments with regard to both molecule metrology and the foundations of quantum mechanics, i.e. the preservation of coherence for highly complex particles in external fields.
The quantum superposition principle, a key distinction between quantum physics and classical mechanics, is often perceived as a philosophical challenge to our concepts of reality, locality or space-time since it contrasts with our intuitive expectations with experimental observations on isolated quantum systems. While we are used to associating the notion of localization with massive bodies, quantum physics teaches us that every individual object is associated with a wave function that may eventually delocalize by far more than the body's own extension. Numerous experiments have verified this concept at the microscopic scale but intuition wavers when it comes to delocalization experiments with complex objects. While quantum science is the uncontested ideal of a physical theory, one may ask if the superposition principle can persist on all complexity scales. This motivates matter-wave diffraction and interference studies with large compounds in a three-grating interferometer configuration which also necessitates the preparation of high-mass nanoparticle beams at low velocities. Here we demonstrate how synthetic chemistry allows us to prepare libraries of fluorous porphyrins which can be tailored to exhibit high mass, good thermal stability and relatively low polarizability, which allows us to form slow thermal beams of these high-mass compounds, which can be detected using electron ionization mass spectrometry. We present successful superposition experiments with selected species from these molecular libraries in a quantum interferometer, which utilizes the diffraction of matter-waves at an optical phase grating. We observe high-contrast quantum fringe patterns of molecules exceeding a mass of 10,000 amu and having 810 atoms in a single particle.
We demonstrate quantum interference for tetraphenylporphyrin, the first biomolecule exhibiting wave nature, and for the fluorofullerene C60F48 using a near-field Talbot-Lau interferometer. For the porphyrins, which are distinguished by their low symmetry and their abundant occurrence in organic systems, we find the theoretically expected maximal interference contrast and its expected dependence on the de Broglie wavelength. For C60F48, the observed fringe visibility is below the expected value, but the high contrast still provides good evidence for the quantum character of the observed fringe pattern. The fluorofullerenes therefore set the new mark in complexity and mass (1632 amu) for de Broglie wave experiments, exceeding the previous mass record by a factor of 2.
This thesis describes theoretical work carried out in connection with the high-mass matter-wave interference experiments at the University of Vienna. Its scope ranges from the simulation and analysis of experimental data to the proposal of a trapped interference scheme applicable to a variety of matter-wave platforms. The first main result of the thesis is the phase-space description of a near-field interferometer with any number of gratings. This theory is used to analyze a four-grating Talbot-Lau interferometer, in which passive compensation of low-frequency vibrations and of the Coriolis force are expected. The compensation is numerically confirmed and its effectiveness is compared to existing techniques. The second main result is the demonstration of Bragg diffraction of complex molecules on optical gratings, to which the author contributed the basic experimental design, simulations, and the interpretation of the data. This demonstration is a first step towards applying large momentum transfer coherent manipulation techniques to the interference of heavy molecules and clusters. The third main result is a new interference scheme for matter waves in toroidal confinement. The beam splitting and recombination in this scheme rely on the free evolution in the waveguide and require no interaction with the matter waves. The scheme is within reach of state-of-the-art experiments with Bose-Einstein condensates, where it could be used to measure weak atom-atom interactions or magnetic field gradients.