Isotope-induced partial localization of core electrons in the homonuclear molecule N2

Rolles, Daniel; Braune, Markus; Cvejanović, S; Geßner, Oliver; Hentges, Rainer; Korica, Sanja; Langer, Burkhard; Lischke, T.; Prümper, G.; Reinköster, Axel; Viefhaus, Jens; Zimmermann, B.; McKoy, Vincent; Becker, Uwe

doi:10.1038/nature04040

Cited by 163 publications

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“…In first approximation, both phase shifts have to be added to describe the β oscillation being proportional to cosðδ þ kRÞ; this is what we observe. This interpretation is supported by studies of the K-shell photoionization of N 2 [3,4,7]. Figure 3(c) shows the angular distribution pattern for N 2 1sonization.…”

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confidence: 63%

“…Measuring the parity-differential cross section allows us to differentiate between the 'gerade' (g, bonding) and 'ungerade' (u, antibonding) molecular orbitals, which are characteristic for inversion symmetric systems. A phase difference of π between g and u orbitals [1,3] results from different signs in their representation as a linear combination of one-electron atomic orbitals of the two molecular sites. Therefore, the interference oscillation phase in σ should provide a pure measure of the molecular parity as it is qualitatively depicted by the schematic description of the coherent superposition from both sites in Fig.…”

mentioning

confidence: 99%

“…It is the absence of "which-way information" that allows for interference. Therefore, most of the existing related studies focus on the inner shells of homonuclear diatomic molecules [2][3][4][5][6][7] to exploit the chemically localized but quantum mechanically nonlocalized character of the core electrons. The nonlocalization allows coherent electron emission from two slits which are fixed and spatially well defined.…”

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Angular Momentum Sensitive Two-Center Interference

et al. 2014

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In quantum mechanics the Young-type double-slit experiment can be performed with electrons either traveling through a double slit or being coherently emitted from two inversion symmetric molecular sites. In the latter one the valence photoionization cross sections of homonuclear diatomic molecules were predicted to oscillate over kinetic energy almost 50 years ago. Beyond the direct proof of the oscillatory behavior of these photoionization cross sections σ, we show that the angular distribution of the emitted electrons reveals hitherto unexplored information on the relative phase shift between the corresponding partial waves through two-center interference patterns. The Young-type double-slit experiment with nonzero mass quantum objects provides a very direct view on wave-particle duality. One way to observe the fundamental quantum nature is provided by electrons being coherently emitted from two inversion symmetric molecular sites. This highly debated molecular double-slit experiment is based on the assumption that coherent electron emission from homonuclear diatomic molecules such as H 2 , N 2 , and O 2 leads to observable interference phenomena in the photoionization cross section of these molecules [1]. Here, the slit distance and the wavelength of Young's classical experiment with photons correspond to the bond length and the de Broglie wavelength of the electron partial wave, respectively. It is the absence of "which-way information" that allows for interference. Therefore, most of the existing related studies focus on the inner shells of homonuclear diatomic molecules [2][3][4][5][6][7] to exploit the chemically localized but quantum mechanically nonlocalized character of the core electrons. The nonlocalization allows coherent electron emission from two slits which are fixed and spatially well defined. However, the fundamental formalism describing the molecular double slit [1] was discussed for the chemically highly delocalized valence states of N 2 and O 2 [1,8]. The basic physics of that work and the numerous K-shell studies are similar for the prediction of the oscillatory behavior of the photoionization partial cross sections σ, which is described in the following equation:Here, σ are the total and partial cross sections for which the angular momentum l denotes the individual angular momentum, Z Ã is the atomic number, k is the electron wave number, R the molecular bond length, and S is the overlap integral for the electrons localized at each site of the molecule. The equation implies that the molecular system absorbs a photon from both possible sites of electron excitation. Recent studies of the molecular double-slit phenomenon in the vibrational branching ratios of molecular photoionization gave the first experimental evidence that the basic model of Cohen and Fano is indeed valid for the valence states [9][10][11]. However, the oscillation of the partial cross sections was never directly observed. In fact, the difference between almost unexplored valence and well studied K-shell double-slit experi...

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Angular Momentum Sensitive Two-Center Interference

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“…Another single channel approach is the Stieltjes-Tchebycheff moment theory (STMT) (CO 47,101 ; N 2 10,30,101,102 ) which is able to describe shape resonances near the ionization threshold (see results below) but suffers from limited energy resolution and range. The Schwinger iterative approach that has been implemented at the frozen core (FCHF) 32,46,48 and relaxed core (RCHF) 14,42,[103][104][105][106] levels for polyatomic molecules can instead produce accurate solutions of the molecular electronic continuum. Another method that has been shown to provide accurate results for large systems is the present multicenter Bspline static-exchange DFT method 17,24,33,49,107 , which makes use of the Kohn-Sham density functional theory to describe the molecular ionic states and the Galerkin approach to evaluate the continuum electron wave function in the field of the corresponding Kohn-Sham density.…”

Section: Theoretical Methods Within the Fixed-nuclei Approximationmentioning

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Vibrational branching ratios in the photoelectron spectra of N2 and CO: interference and diffraction effects

Plésiat

Decleva

Martín

2012

Phys. Chem. Chem. Phys.

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Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in: We present a detailed account of existing theoretical methods specially designed to provide vibrationally resolved photoionization cross sections of simple molecules within the Born-Oppenheimer approximation, with emphasis on newly developed methods based on density functional theory. The performance of these methods is shown for the case of N 2 and CO photoionization. Particular attention is paid to the region of high photon energies, where the electron wavelength is comparable to the bond length and, therefore, two-center interferences and diffraction are expected to occur. As shown in a recent work [Canton et al., Proc. Natl. Acad. Sci., 2011, 108, 73027306], the main experimental difficulty, which is to extract the relatively small diffraction features from the rapidly decreasing cross section, can be easily overcome by determining ratios of vibrationally resolved photoelectron spectra and existing theoretical calculations. From these ratios, one can thus get direct information about the molecular geometry. In this work, results obtained in a wide range of photon energies and for many different molecular orbitals of N 2 and CO are discussed and compared with the available experimental measurements. From this comparison, limitations and further possible improvements of the existing theoretical methods are discussed. The new results presented in the manuscript confirm that the conclusions reported in the above reference are of general validity.

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“…N 2 represents one of the simplest few-electron diatomic systems, and its interaction with light has been extensively studied experimentally as well as theoretically. A wealth of results has been reported for single-photon interactions (see, e.g., [86,[112][113][114][115][116][117][118][119], fragmentation by intense laser fields [83,84], two-colour time-resolved studies [73], and highresolution electron impact coincidence measurements [120]. Recently, several experiments on multiple ionization of N 2 by few EUV photons have been performed at FLASH and SCSS.…”

Section: Multiple Fragmentation Of N 2 Moleculementioning

confidence: 99%

Exploring few-photon, few-electron reactions at FLASH: from ion yield and momentum measurements to time-resolved and kinematically complete experiments

Rudenko

Jiang

Курка

et al. 2010

J. Phys. B: At. Mol. Opt. Phys.

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Abstract:In this contribution we briefly review a series of recent pioneering experiments on fewphoton-induced multiple fragmentation of atoms and molecules performed at the Free electron LASer at Hamburg (FLASH) using a "Reaction Microscope", i.e., a coincident momentum imaging technique. For atoms we consider the most basic non-linear process, namely direct or sequential two-photon double ionization (TPDI). In particular benchmark data for theory are presented such as recoil-ion momentum distributions for direct TPDI of He and Ne, and fully differential data for sequential TPDI of Ne. For molecules we show how one can identify contributions from different reaction channels by inspecting the measured kinetic energy and angular distributions of ionic fragments, and even infer the time-delay between the two photon absorption events in TPDI by detailed comparison with theory.Finally, we describe a novel split mirror arrangement for EUV-pump -EUV-probe experiments, and present the very first time-resolved data on the dynamics of N 2 molecules irradiated by the FLASH light.

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Isotope-induced partial localization of core electrons in the homonuclear molecule N2

Cited by 163 publications

References 31 publications

Angular Momentum Sensitive Two-Center Interference

Angular Momentum Sensitive Two-Center Interference

Vibrational branching ratios in the photoelectron spectra of N2 and CO: interference and diffraction effects

Exploring few-photon, few-electron reactions at FLASH: from ion yield and momentum measurements to time-resolved and kinematically complete experiments

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