171 research outputs found
Towards quantum superpositions of a mirror
We propose a scheme for creating quantum superposition states involving of
order atoms via the interaction of a single photon with a tiny
mirror. This mirror, mounted on a high-quality mechanical oscillator, is part
of a high-finesse optical cavity which forms one arm of a Michelson
interferometer. By observing the interference of the photon only, one can study
the creation and decoherence of superpositions involving the mirror. All
experimental requirements appear to be within reach of current technology.Comment: 5 pages, 2 figures, submitted to Phys. Rev. Let
Inelastic Diffraction and Spectroscopy of Very Weakly Bound Clusters
We study the coherent inelastic diffraction of very weakly bound two body
clusters from a material transmission grating. We show that internal
transitions of the clusters can lead to new separate peaks in the diffraction
pattern whose angular positions determine the excitation energies. Using a
quantum mechanical approach to few body scattering theory we determine the
relative peak intensities for the diffraction of the van der Waals dimers
(D_2)_2 and H_2-D_2. Based on the results for these realistic examples we
discuss the possible applications and experimental challenges of this coherent
inelastic diffraction technique.Comment: 15 pages + 5 figures. J. Phys. B (in press
Cryogenic infrared spectroscopy provides mechanistic insight into the fragmentation of phospholipid silver adducts
Tandem mass spectrometry is arguably the most important analytical tool for structure elucidation of lipids and other metabolites. By fragmenting intact lipid ions, valuable structural information such as the lipid class and fatty acyl composition are readily obtainable. The information content of a fragment spectrum can often be increased by the addition of metal cations. In particular, the use of silver ions is deeply rooted in the history of lipidomics due to their propensity to coordinate both electron-rich heteroatoms and C = C bonds in aliphatic chains. Not surprisingly, coordination of silver ions was found to enable the distinction of sn-isomers in glycerolipids by inducing reproducible intensity differences in the fragment spectra, which could, however, not be rationalized. Here, we investigate the fragmentation behaviors of silver-adducted sn- and double bond glycerophospholipid isomers by probing fragment structures using cryogenic gas-phase infrared (IR) spectroscopy. Our results confirm that neutral headgroup loss from silver-adducted glycerophospholipids leads to dioxolane-type fragments generated by intramolecular cyclization. By combining high-resolution IR spectroscopy and computational modelling of silver-adducted fragments, we offer qualitative explanations for different fragmentation behaviors of glycerophospholipid isomers. Overall, the results demonstrate that gas-phase IR spectroscopy of fragment ions can significantly contribute to our understanding of lipid dissociation mechanisms and the influence of coordinating cations
Quantum Theory Approach for Neutron Single and Double-Slit Diffraction
We provide a quantum approach description of neutron single and double-slit
diffraction, with specific attention to the cold neutron diffraction (\AA) carried out by Zeilinger et al. in 1988. We find the
theoretical results are good agreement with experimental data.Comment: 10 page
Unveiling Glycerolipid Fragmentation by Cryogenic Infrared Spectroscopy
Mass spectrometry is routinely employed for structure elucidation of molecules. Structural information can be retrieved from intact molecular ions by fragmentation; however, the interpretation of fragment spectra is often hampered by poor understanding of the underlying dissociation mechanisms. For example, neutral headgroup loss from protonated glycerolipids has been postulated to proceed via an intramolecular ring closure but the mechanism and resulting ring size have never been experimentally confirmed. Here we use cryogenic gas-phase infrared (IR) spectroscopy in combination with computational chemistry to unravel the structures of fragment ions and thereby shed light on elusive dissociation mechanisms. Using the example of glycerolipid fragmentation, we study the formation of protonated five-membered dioxolane and six-membered dioxane rings and show that dioxolane rings are predominant throughout different glycerolipid classes and fragmentation channels. For comparison, pure dioxolane and dioxane ions were generated from tailor-made dehydroxyl derivatives inspired by natural 1,2- and 1,3-diacylglycerols and subsequently interrogated using IR spectroscopy. Furthermore, the cyclic structure of an intermediate fragment occurring in the phosphatidylcholine fragmentation pathway was spectroscopically confirmed. Overall, the results contribute substantially to the understanding of glycerolipid fragmentation and showcase the value of vibrational ion spectroscopy to mechanistically elucidate crucial fragmentation pathways in lipidomics
Studying the Key Intermediate of RNA Autohydrolysis by Cryogenic Gas-Phase Infrared Spectroscopy
Over the course of the COVID-19 pandemic, mRNA-basedvaccineshave gained tremendous importance. The development and analysis of modified RNA moleculesbenefit from advanced mass spectrometry and require sufficient understanding of fragmentation processes.Analogous tothe degradation of RNA in solution by autohydrolysis,backbone cleavage of RNA strands wasequally observedin the gas phase; however, the fragmentation mechanism remained elusive.In this work,autohydrolysis-like intermediates weregenerated from isolated RNA dinucleotidesin the gas phaseand investigatedusing cryogenic infrared spectroscopy in helium nanodroplets.Data from both experiment and density functional theory provide evidence forthe formation of a five-membered cyclic phosphateintermediateand rule outlinear orsix-membered structures. Furthermore, the experiments show that another prominent condensed-phase reactionof RNA nucleotides can be induced in the gas phase: the tautomerization of cytosine.Both observed reactions aretherefore highlyuniversal and intrinsic properties of the investigated molecules
The size of two-body weakly bound objects : short versus long range potentials
The variation of the size of two-body objects is investigated, as the
separation energy approaches zero, with both long range potentials and short
range potentials having a repulsive core. It is shown that long range
potentials can also give rise to very extended systems. The asymptotic laws
derived for states with angular momentum l=1,2 differ from the ones obtained
with short range potentials. The sensitivity of the asymptotic laws on the
shape and length of short range potentials defined by two and three parameters
is studied. These ideas as well as the transition from the short to the long
range regime for the l=0 case are illustrated using the Kratzer potential.Comment: 5 pages, 3 figures, submitted to Physical Review Letter
Untersuchung des reaktiven Intermediats der RNA Autohydrolyse mittels kryogener Infrarotspektroskopie in der Gasphase
Im Laufe der COVID-19 Pandemie haben mRNA-basierte Impfstoffe an immenser Bedeutung gewonnen. Massenspektrometrie ist für die Entwicklung und Analyse von modifizierten RNA Molekülen unerlässlich, setzt jedoch ein grundlegendes Verständnis über Fragmentierungsprozesse voraus. Analog zu der Zersetzung von RNA in Lösung durch Autohydrolyse, kann die Spaltung des RNA Rückgrats ebenso in der Gasphase stattfinden. Bislang sind die Fragmentierungsmechanismen jedoch unzureichend untersucht. In dieser Arbeit wurden Intermediate aus isolierten RNA Dinukleotiden in der Gasphase generiert und mittels kryogener Infrarotspektroskopie in Helium-Nanotröpfchen untersucht. Die experimentellen Daten, unterstützt durch Dichtefunktionaltheorie, liefern Hinweise dafür, dass die Bildung eines fünfgliedrigen zyklischen Phosphat-Intermediats begünstigt ist, während lineare oder sechsgliedrige Strukturen ausgeschlossen werden können. Weiterhin zeigen die Experimente, dass eine zusätzliche, bekannte Reaktion von RNA Nukleotiden in Lösung auch in der Gasphase induziert werden kann: die Tautomerisierung von Cytosin. Die beiden beobachteten Reaktionen spiegeln daher universelle und intrinsische Eigenschaften der untersuchten Moleküle wider
Site-specific vibrational spectral signatures of water molecules in the magic H<sub>3</sub>O<sup>+</sup>(H<sub>2</sub>O)<sub>20</sub> and Cs<sup>+</sup>(H<sub>2</sub>O)<sub>20</sub> clusters
Theoretical models of proton hydration with tens of water molecules indicate that the excess proton is embedded on the surface of clathrate-like cage structures with one or two water molecules in the interior. The evidence for these structures has been indirect, however, because the experimental spectra in the critical H-bonding region of the OH stretching vibrations have been too diffuse to provide band patterns that distinguish between candidate structures predicted theoretically. Here we exploit the slow cooling afforded by cryogenic ion trapping, alongwith isotopic substitution, to quench water clusters attached to the H3O+ and Cs+ ions into structures that yield well-resolved vibrational bands over the entire 215- to 3,800-cm−1 range. The magic H3O+ (H2O)20 cluster yields particularly clear spectral signatures that can, with the aid of ab initio predictions, be traced to specific classes of network sites in the predicted pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the surface
Velocity-selective sublevel resonance of atoms with an array of current-carrying wires
Resonance transitions between the Zeeman sublevels of optically-polarized Rb
atoms traveling through a spatially periodic magnetic field are investigated in
a radio-frequency (rf) range of sub-MHz. The atomic motion induces the
resonance when the Zeeman splitting is equal to the frequency at which the
moving atoms feel the magnetic field oscillating. Additional temporal
oscillation of the spatially periodic field splits a motion-induced resonance
peak into two by an amount of this oscillation frequency. At higher oscillation
frequencies, it is more suitable to consider that the resonance is mainly
driven by the temporal field oscillation, with its velocity-dependence or
Doppler shift caused by the atomic motion through the periodic field. A
theoretical description of motion-induced resonance is also given, with
emphasis on the translational energy change associated with the internal
transition.Comment: 7 pages, 3 figures, final versio
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