The thesis aimed to identify chemical modifications for biomolecules such as peptides and proteins to make these amenable for matter‐wave interference experiments. Crucial for matter‐wave interference experiments are charge neutral biomolecular beams, which had previously only been successfully formed for small peptides in a limited number of studies. Accordingly, a main focus of the thesis was set on the formation of such beams in close collaboration with M. Arndt's group in Vienna. A second difficulty arises from the fact that neutral molecules are not detectable with common mass spectrometer detectors, i.e. electron multipliers. Consequently the ionization of neutral protein beams in high vacuum was a second central point of the presented studies. Various methods and approaches were investigated whereby the contribution of the author was concentrated on the design, synthesis and expression of the constructs for interrogation in matterwave experiments.
The thesis aimed to identify chemical modifications for biomolecules such as peptides and proteins to make these amenable for matter‐wave interference experiments. Crucial for matter‐wave interference experiments are charge neutral biomolecular beams, which had previously only been successfully formed for small peptides in a limited number of studies. Accordingly, a main focus of the thesis was set on the formation of such beams in close collaboration with M. Arndt's group in Vienna. A second difficulty arises from the fact that neutral molecules are not detectable with common mass spectrometer detectors, i.e. electron multipliers. Consequently the ionization of neutral protein beams in high vacuum was a second central point of the presented studies. Various methods and approaches were investigated whereby the contribution of the author was concentrated on the design, synthesis and expression of the constructs for interrogation in matterwave experiments.
These lecture notes emerged from a contribution to the "Les Houches Summer School, Session CVII - Current Trends in Atomic Physics, July 2016". It is meant to serve students as a guide to a selection of topics that are currently at the focus of molecular quantum optics and complements an earlier lecture on related topics [Arndt et al., 2014]. In this review we discuss recent advances in molecular quantum optics with large organic molecules. In particular, we present successful experiments of molecules of biological importance, such as neurotransmitters and map out the route towards interferometry of large bio-matter such as proteins. The interaction of internally complex molecules with various beam splitters is discussed for both far-field diffraction at a single nanomechanical grating and the Kapitza-Dirac Talbot-Lau near-field interferometer - addressing recent progress, experimental challenges, and prospects for quantum enhanced metrology of highly complex systems in the gas phase. A central part of this review deals with the preparation of slow beams of neutral biomolecules, ranging from a single amino acid to proteins or peptides in a micro-environment.
We study the optical properties of various large molecules with respect to their suitability for new matter wave interference and detection schemes. Optical phase gratings for molecules will only be compatible with a sufficiently small absorption cross section visible while optical detection schemes may exploit strong UV resonances. We compare UV-VIS spectra of various biomolecules, such as amino acids, polypeptides, and proteins, with those of new perfluoroalkylated molecules and carbon nanotubes, and we discuss their suitability for coherent matter wave experiments.
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
Modern quantum optics encompasses a wide field of phenomena that are either related to the discrete quantum nature of light, the quantum wave nature of matter or light-matter interactions.We here discuss new perspectives for quantum optics with biological nanoparticles.We focus in particular on the prospects of matter-wave interferometry with amino acids, nucleotides, polypeptides or DNA strands.We motivate the challenge of preparing these objects in a 'biomimetic' environment and argue that hydrated molecular beam sources are promising tools for quantum-assisted metrology.The method exploits the high sensitivity of matter-wave interference fringes to dephasing and shifts in the presence of external perturbations to access and determine molecular properties.
The chapter discusses advances in matter-wave optics with complex molecules, generalizing Young’s double slit to high masses. The quantum wave-particle duality is visualized by monitoring the arrival patterns of molecules diffracted at nanomechanical masks. Each molecule displays particle behavior when it is localized on the detector; however, the overall interference pattern requires their delocalization in free flight. Internal particle properties influence the de Broglie waves in the presence of surfaces or fields—even in interaction with atomically thin gratings. To probe the quantum nature of high-mass molecules, universal beam splitters are combined in a multi-grating interferometer to observe high-contrast matter-wave fringes even for 500 K hot molecules, containing 810 atoms with a mass of 10 000 amu. The high sensitivity of the nanoscale interference fringes to deflection in external fields enables non-invasive measurements of molecular properties. The chapter concludes by discussing research on beam techniques that extend molecular quantum optics to large biomolecules.
We describe the state of the art in preparing, manipulating and detecting coherent molecular matter. We focus on experimental methods for handling the quantum motion of compound systems from diatomic molecules to clusters or biomolecules.Molecular quantum optics offers many challenges and innovative prospects: already the combination of two atoms into one molecule takes several well-established methods from atomic physics, such as for instance laser cooling, to their limits. The enormous internal complexity that arises when hundreds or thousands of atoms are bound in a single organic molecule, cluster or nanocrystal provides a richness that can only be tackled by combining methods from atomic physics, chemistry, cluster physics, nanotechnology and the life sciences.We review various molecular beam sources and their suitability for matter-wave experiments. We discuss numerous molecular detection schemes and give an overview over diffraction and interference experiments that have already been performed with molecules or clusters.Applications of de Broglie studies with composite systems range from fundamental tests of physics up to quantum-enhanced metrology in physical chemistry, biophysics and the surface sciences.Nanoparticle quantum optics is a growing field, which will intrigue researchers still for many years to come. This review can, therefore, only be a snapshot of a very dynamical process.