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1.
J Phys Chem A ; 2020 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-32463669

RESUMO

Electronic excitations in the valence shell of Ne clusters were studied by fluorescence spectroscopy. The measured fluorescence excitation functions contain information about the nature and number of excitonic states and the mean cluster size of the produced size distribution. Mean cluster sizes were determined by comparing surface and bulk contributions using a multidimensional fitting algorithm, with good agreement to commonly used scaling laws. The influence of different size distributions, which were not considered in previous investigations on homogeneous noble gas cluster jets, are implemented into the proposed model. The present work is the first approach using fluorescence spectroscopy for the determination of the mean size of Ne cluster jets created by supersonic expansion.

2.
Phys Rev Lett ; 123(21): 213001, 2019 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-31809166

RESUMO

We report the observation of the radiative decay of singly charged noble gas ground-state ions embedded in heterogeneous van der Waals clusters. Electron-photon coincidence spectroscopy and dispersed photon spectroscopy are applied to identify the radiative charge transfer from Kr atoms to a Ne_{2}^{+} dimer, which forms after single valence photoionization of Ne atoms at the surface of a NeKr cluster. This mechanism might be a fundamental decay process of ionized systems in an environment.

4.
J Am Chem Soc ; 141(30): 12029-12043, 2019 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-31268701

RESUMO

Enzymes are Nature's polyfunctional catalysts tailor-made for specific biochemical synthetic transformations, which often proceed with almost perfect stereocontrol. From a synthetic point of view, artificial catalysts usually offer the advantage of much broader substrate scopes, but stereocontrol is often inferior to that possible with natural enzymes. A particularly difficult synthetic task in asymmetric catalysis is to overwrite a pronounced preference for the formation of an inherently favored diastereomer; this requires a high level of stereocontrol. In this Article, the development of a novel artificial polyfunctional catalyst type is described, in which an imidazolium-aryloxide betaine moiety cooperates with a Lewis acidic metal center (here Cu(II)) within a chiral catalyst framework. This strategy permits for the first time a general, highly enantioselective access to the otherwise rare diastereomer in the direct 1,4-addition of various 1,3-dicarbonyl substrates to ß-substituted nitroolefins. The unique stereocontrol by the polyfunctional catalyst system is also demonstrated with the highly stereoselective formation of a third contiguous stereocenter making use of a diastereoselective nitronate protonation employing α,ß-disubstituted nitroolefin substrates. Asymmetric 1,4-additions of ß-ketoesters to α,ß-disubstituted nitroolefins have never been reported before in literature. Combined mechanistic investigations including detailed spectroscopic and density functional theory (DFT) studies suggest that the aryloxide acts as a base to form a Cu(II)-bound enolate, whereas the nitroolefin is activated by H-bonds to the imidazolium unit and the phenolic OH generated during the proton transfer. Detailed kinetic analyses (RPKA, VTNA) suggest that (a) the catalyst is stable during the catalytic reaction, (b) not inhibited by product and (c) the rate-limiting step is most likely the C-C bond formation in agreement with the DFT calculations of the catalytic cycle. The robust catalyst is readily synthesized and recyclable and could also be applied to a cascade cyclization.

5.
J Phys Chem Lett ; 10(5): 1078-1082, 2019 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-30779875

RESUMO

Energy and charge transfer processes play an important role in many fundamental reactions in chemistry, biochemistry, and even technology. If an entity that is part of a larger system is photoexcited, its energy will dissipate, for example, by rearrangement of electron density in a large molecule or by photon emission (fluorescence). Here, we report the experimental observation of free electrons from a heterogeneous van der Waals cluster, in which some sites act as electron emitters receiving their energy efficiently from other "antenna" sites that are resonantly excited in the UV range. By complementing electron spectroscopy with fluorescence detection, we can directly observe that electron emission via this mechanism completely quenches fluorescence once the channel opens. We suggest this mechanism to be important for both quenching of fluorescence as well as resonantly enhancing free electron production in a variety of systems.

7.
Molecules ; 23(7)2018 06 26.
Artigo em Inglês | MEDLINE | ID: mdl-29949868

RESUMO

Dichroism in angle-resolved spectra of circularly polarized fluorescence from freely-rotating CO molecules was studied experimentally and theoretically. For this purpose, carbon monoxide in the gas phase was exposed to circularly polarized soft X-ray synchrotron radiation. The photon energy was tuned across the C 1s→π* resonant excitation, which decayed via the participator Auger transition into the CO⁺ A ²Π state. The dichroic parameter ß1 of the subsequent CO⁺ (A ²Π → X ²Σ⁺) visible fluorescence was measured by photon-induced fluorescence spectroscopy. Present experimental results are explained with the ab initio electronic structure and dynamics calculations performed by the single center method. Our results confirm the possibility to perform partial wave analysis of the emitted photoelectrons in closed-shell molecules.


Assuntos
Monóxido de Carbono/química , Dicroísmo Circular , Modelos Teóricos , Espectrometria de Fluorescência
8.
Materials (Basel) ; 11(6)2018 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-29789512

RESUMO

The detection of a single photon is the most sensitive method for sensing of photon emission. A common technique for single photon detection uses microchannel plate arrays combined with photocathodes and position sensitive anodes. Here, we report on the combination of such detectors with grating diffraction spectrometers, constituting a low-noise wavelength resolving photon spectroscopy apparatus with versatile applicability. We recapitulate the operation principle of such detectors and present the details of the experimental set-up, which we use to investigate fundamental mechanisms in atomic and molecular systems after excitation with tuneable synchrotron radiation. Extensions for time and polarization resolved measurements are described and examples of recent applications in current research are given.

9.
J Phys Chem Lett ; 8(13): 2780-2786, 2017 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-28582620

RESUMO

Most large molecules are chiral in their structure: they exist as two enantiomers, which are mirror images of each other. Whereas the rovibronic sublevels of two enantiomers are almost identical (neglecting a minuscular effect of the weak interaction), it turns out that the photoelectric effect is sensitive to the absolute configuration of the ionized enantiomer. Indeed, photoionization of randomly oriented enantiomers by left or right circularly polarized light results in a slightly different electron flux parallel or antiparallel with respect to the photon propagation direction-an effect termed photoelectron circular dichroism (PECD). Our comprehensive study demonstrates that the origin of PECD can be found in the molecular frame electron emission pattern connecting PECD to other fundamental photophysical effects such as the circular dichroism in angular distributions (CDAD). Accordingly, distinct spatial orientations of a chiral molecule enhance the PECD by a factor of about 10.

10.
J Phys Chem B ; 121(10): 2326-2330, 2017 03 16.
Artigo em Inglês | MEDLINE | ID: mdl-28187257

RESUMO

Despite its importance, the structure and dynamics of liquid water are still poorly understood in many apsects. Here, we report on the observation of optical fluorescence upon soft X-ray irradiation of liquid water. Detection of spectrally resolved fluorescence was achieved by a combination of the liquid microjet technique and fluorescence spectroscopy. We observe a genuine liquid-phase fluorescence manifested by a broad emission band in the 170-340 nm (4-7 eV) photon wavelength range. In addition, another narrower emission near 300 nm can be assigned to the fluorescence of OH (A state) in the gas phase, the emitting species being formed by Auger electrons escaping from liquid water. We argue that the newly observed broad-band emission of liquid water is relevant in search of extraterrestrial life, and we also envision the observed electron-ejection mechanism to find application for exploring solutes at liquid-vapor interfaces.

11.
Phys Rev Lett ; 98(3): 036602, 2007 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-17358706

RESUMO

We show that the joint effect of spin-orbit and magnetic fields leads to a spin polarization perpendicular to the plane of a homogeneous two-dimensional electron system with Rashba spin-orbit coupling and in-plane parallel dc magnetic and electric fields, for angle-dependent impurity scattering or nonparabolic energy spectrum, while only in-plane polarization persists for simplified models. We derive Bloch equations, describing the main features of recent experiments, including the magnetic field dependence of static and dynamic responses.

12.
Ultramicroscopy ; 107(2-3): 202-12, 2007.
Artigo em Inglês | MEDLINE | ID: mdl-16989948

RESUMO

A theoretical description of the contrast-imaging function is derived for tilted specimens that exhibit weak-phase object characteristics. We show that the tilted contrast-imaging function (TCIF) is a linear transformation, which can be approximated by the convolution operation for small tilt angles or for small specimens. This approximation is not valid for electron tomography, where specimen tilts are above 60 degrees and specimen dimensions amount to some 10 microm. The approximation also breaks down for electron crystallography, where atomic resolution is to be achieved. Therefore, we do not make this approximation and propose a generalized algorithm for inverting the TCIF. The implications of our description are discussed in the context of electron tomography, single particle analysis, and electron crystallography, and the improved resolution is quantitatively demonstrated.


Assuntos
Microscopia Eletrônica/métodos , Cristalografia , Processamento de Imagem Assistida por Computador , Tomografia
13.
Phys Rev Lett ; 95(16): 166605, 2005 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-16241829

RESUMO

We develop a theory of extrinsic spin currents in semiconductors, resulting from spin-orbit coupling at charged scatterers, which leads to skew-scattering and side-jump contributions to the spin-Hall conductivity. Applying the theory to bulk n-GaAs, without any free parameters, we find spin currents that are in reasonable agreement with experiments by Kato et al. [Science 306, 1910 (2004)].

14.
Science ; 309(5734): 586-8, 2005 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-16040700

RESUMO

We propose a protocol and physical implementation for partial Bell-state measurements of Fermionic qubits, allowing for deterministic quantum computing in solid-state systems without the need for two-qubit gates. Our scheme consists of two spin qubits in a double quantum dot where the two dots have different Zeeman splittings and resonant tunneling between the dots is only allowed when the spins are antiparallel. This converts spin parity into charge information by means of a projective measurement and can be implemented with established technologies. This measurement-based qubit scheme greatly simplifies the experimental realization of scalable quantum computers in electronic nanostructures.

15.
Phys Rev Lett ; 93(13): 136602, 2004 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-15524748

RESUMO

We analyze the frequency-dependent noise of a current through a quantum dot which is coupled to Fermi leads and which is in the Coulomb blockade regime. We show that the asymmetric shot noise, as a function of detection frequency, shows steps and becomes super-Poissonian. This provides experimental access to the quantum fluctuations of the current. We present an exact calculation of the noise for a single dot level and a perturbative evaluation of the noise in Born approximation (sequential tunneling regime but without Markov approximation) for the general case of many levels with charging interaction.

16.
Phys Rev Lett ; 93(10): 106804, 2004 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-15447437

RESUMO

We consider electron spin qubits in quantum dots and define a measurement efficiency e to characterize reliable measurements via n-shot readouts. We propose various implementations based on a double dot and a quantum point contact (QPC) and show that the associated efficiencies e vary between 50% and 100%, allowing single-shot readout in the latter case. We model the readout microscopically and derive its time dynamics in terms of a generalized master equation, calculate the QPC current, and show that it allows spin readout under realistic conditions.

17.
Eur Biophys J ; 31(3): 172-8, 2002 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-12029329

RESUMO

The atomic force microscope acquires topographs of single native membrane proteins at subnanometer resolution. Owing to the high signal-to-noise ratio, such images allow the conformational space of membrane protein surfaces to be sampled. This is demonstrated by topographs of porin OmpF, aquaporin-Z, and bacteriorhodopsin, all recorded at a lateral resolution of <7 A and a vertical resolution of ~1 A. The amplitudes of the domain movements were estimated from a large number of single molecule topographs and the corresponding energy landscapes calculated. To visualize the motion of protein domains, movies were generated by similarity ranking of the observed protein configurations. Electronic supplementary material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00249-001-0197-8


Assuntos
Proteínas de Escherichia coli , Aumento da Imagem/métodos , Imageamento Tridimensional/métodos , Proteínas de Membrana/química , Microscopia de Força Atômica/métodos , Nanotecnologia , Aquaporinas/química , Bacteriorodopsinas/química , Movimento (Física) , Porinas/química , Conformação Proteica
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