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Interatomic Coulombic Decay (ICD) and related interatomic and intermolecular autoionization mechanisms are ubiquitous decay processes of excited atoms and molecules in an environment. It is commonly accepted that the efficiency of ICD of an ionized atom in a cluster increases with an increasing number of nearest neighbors. Here, we present a method for experimental validation of this assumption by a site-specific and quantitative comparison of ICD and its main competitor, Auger decay, in core-level ionized Kr clusters. Our results are in quantitative agreement with scaled theoretical calculations on Kr2.

Ab initio simulations are employed to assess the interaction of typical interstitial impurities with self-interstitial atoms, dislocation loops and edge dislocation lines in tungsten. These impurities are present in commercial tungsten grades and are also created as a result of neutron transmutation or the plasma in-take process. The relevance of the study is determined by the application of tungsten as first wall material in fusion reactors. For the defects with dislocation character, the following ordering of the interaction strength was established: H

Nature Communications 12(1), 1638 (2021). doi:10.1038/s41467-021-21756-6, Key insights in materials at extreme temperatures and pressures can be gained by accurate measurements that determine the electrical conductivity. Free-electron laser pulses can ionize and excite matter out of equilibrium on femtosecond time scales, modifying the electronic and ionic structures and enhancing electronic scattering properties. The transient evolution of the conductivity manifests the energy coupling from high temperature electrons to low temperature ions. Here we combine accelerator-based, high-brightness multi-cycle terahertz radiation with a single-shot electro-optic sampling technique to probe the evolution of DC electrical conductivity using terahertz transmission measurements on sub-picosecond time scales with a multi-undulator free electron laser. Our results allow the direct determination of the electron-electron and electron-ion scattering frequencies that are the major contributors of the electrical resistivity., Published by Nature Publishing Group UK, [London]

Quasi-two-dimensional perovskites have emerged as a new material platform for optoelectronics on account of its intrinsic stability. A major bottleneck to device performance is the high charge injection barrier caused by organic molecular layers on its basal plane, thus the best performing device currently relies on edge contact. Herein, by leveraging on van der Waals coupling and energy level matching between two-dimensional Ruddlesden-Popper perovskite and graphene, we show that the plane-contacted perovskite and graphene interface presents a lower barrier than gold for charge injection. Electron tunneling across the interface occurs via a gate-tunable, direct tunneling-to-field emission mechanism with increasing bias, and photoinduced charge transfer occurs at femtosecond timescale (~50 fs). Field effect transistors fabricated on molecularly thin Ruddlesden-Popper perovskite using graphene contact exhibit electron mobilities ranging from 0.1 to 0.018 cm2V−1s−1 between 1.7 to 200 K. Scanning tunneling spectroscopy studies reveal layer-dependent tunneling barrier and domain size on few-layered Ruddlesden-Popper perovskite., Insulating molecular layers on the basal plane of 2D perovskite is a major bottleneck for charge injection that limiting device performance. Here, the authors show that plane-contacted graphene functions as a low barrier and gate-tunable contact to overcome this limitation.

Trapped molecular ions in pure rovibronic states are desirable in experiments ranging from cold chemistry to searches for physics beyond the Standard Model. Resonance-enhanced multiphoton ionisation (REMPI) can be used to prepare molecular ions in specific internal states with high fidelities. However, in the presence of electric fields, ionisation spectra exhibit frequency shifts and the ionisation thresholds are broadened. For this reason, REMPI studies are normally conducted in low and highly homogeneous electric fields, whereas the operating principle of rf ion traps requires electric fields that vary in space and time. In order to investigate the impact of this on the state-selectivity of REMPI in ion traps, we have simulated the expected broadening of the ionisation threshold under various operating conditions of a typical linear Paul trap. In many cases, the width of the ionisation threshold exceeds the separation between rotational energy levels, preventing state-selective ionisation. Careful choice of the trapping and laser parameters during loading can reduce this broadening, enabling state-selective ionisation in some instances. Where this strategy is not sufficient, the broadening can be reduced further by rapidly switching the trapping voltages off and on again during loading. This has been demonstrated experimentally for a Coulomb crystal of $$^{40}\hbox {Ca}^+$$ 40 Ca + ions without descrystallising it.

Extreme ultraviolet (EUV) lithography is currently entering high-volume manufacturing to enable the continued miniaturization of semiconductor devices. The required EUV light, at 13.5 nm wavelength, is produced in a hot and dense laser-driven tin plasma. The atomic origins of this light are demonstrably poorly understood. Here we calculate detailed tin opacity spectra using the Los Alamos atomic physics suite ATOMIC and validate these calculations with experimental comparisons. Our key finding is that EUV light largely originates from transitions between multiply-excited states, and not from the singly-excited states decaying to the ground state as is the current paradigm. Moreover, we find that transitions between these multiply-excited states also contribute in the same narrow window around 13.5 nm as those originating from singly-excited states, and this striking property holds over a wide range of charge states. We thus reveal the doubly magic behavior of tin and the origins of the EUV light., Extreme ultraviolet (EUV) light is entering use in nanolithography. Here the authors discuss experimental and theoretical results about the prominent role of multiply-excited states in highly charged tin ions in the mechanism of EUV light emission from laser-produced plasma.

The Kondo effect offers an important paradigm to understand strongly correlated many-body physics. Although under intensive study, some of the important properties of the Kondo effect, in systems where both itinerant coupling and localized coupling play significant roles, are still elusive. Here we report the evolution and universality of the two-stage Kondo effect, the simplest form where both couplings are important using single molecule transistor devices incorporating Manganese phthalocyanine molecules. The Kondo temperature T* of the two-stage Kondo effect evolves linearly against effective interaction of involved two spins. Observed Kondo resonance shows universal quadratic dependence with all adjustable parameters: temperature, magnetic field and biased voltages. The difference in nonequilibrium conductance of two-stage Kondo effect to spin 1/2 Kondo effect is also identified. Messages learned in this study fill in directive experimental evidence of the evolution of two-stage Kondo resonance near a quantum phase transition point, and help in understanding sophisticated molecular electron spectroscopy in a strong correlation regime.

We propose a novel and simple method for the laser isotope separation of 176Lu a precursor for the production of 177Lu medical isotope. The physics of the laser-atom interaction has been studied through the dynamics of the atomic level populations using the density matrix formalism. It has been shown that a combination of cw excitation lasers and pulsed ionization laser can be used for the laser isotope separation of 176Lu. The optimum conditions for the efficient and selective separation of 176Lu have been derived by studying the time evolution of level population under laser excitation. It has also been shown that, it might be possible to produce ~ 100% enriched 176Lu isotope at a rate of 5 mg/h, which is higher than all previously reported methods so far. The isotope separation process proposed can be easily adopted using off-the-shelf lasers, for similar atomic systems.

We report on a transition in a monolayer of C60 molecules deposited on a WO2/W(110) substrate. The transition from a static state, where the molecules are rigidly bound to the surface by a coordination bond, to a state where the molecules are loosely bound to the surface by van der Waals force and rotate continuously, has been studied using scanning tunnelling microscopy (STM). The separation between the molecules and the surface increases by 1.2 Å across the transition. The transition from the static state into the rotating state takes place at 259 K. The energy of the spinning state with respect to the lowest energy state, having a single coordinated bond, can be obtained from the statistics of the molecules switching. The binding energy of the molecule in the spinning state can be easily altered by changing the polarity of the bias voltage applied between the STM tip and the surface. The binding energy decreases by 80 meV when the bias polarity of the sample changes from positive to negative with respect to the tip. The results are consistent with the Coulomb blockade model: when electrons travel from the surface to the C60 molecule, and then to the tip; charge accumulates on the molecule due to the Coulomb blockade. This increases the electrostatic interaction between the molecule’s charge and a corresponding image charge generated on the metallic surface.

Nuclear quantum effects (NQE) tend to generate delocalized molecular dynamics due to the inclusion of the zero point energy and its coupling with the anharmonicities in interatomic interactions. Here, we present evidence that NQE often enhance electronic interactions and, in turn, can result in dynamical molecular stabilization at finite temperature. The underlying physical mechanism promoted by NQE depends on the particular interaction under consideration. First, the effective reduction of interatomic distances between functional groups within a molecule can enhance the $n\to\pi^*$ interaction by increasing the overlap between molecular orbitals or by strengthening electrostatic interactions between neighboring charge densities. Second, NQE can localize methyl rotors by temporarily changing molecular bond orders and leading to the emergence of localized transient rotor states. Third, for noncovalent van der Waals interactions the strengthening comes from the increase of the polarizability given the expanded average interatomic distances induced by NQE. The implications of these boosted interactions include counterintuitive hydroxyl--hydroxyl bonding, hindered methyl rotor dynamics, and molecular stiffening which generates smoother free-energy surfaces. Our findings yield new insights into the versatile role of nuclear quantum fluctuations in molecules and materials., Comment: 10 pages, 5 figures, research article

Nature Communications 12(1), 6657 (2021). doi:10.1038/s41467-021-26994-2, How long does it take to emit an electron from an atom? This question has intrigued scientists for decades. As such emission times are in the attosecond regime, the advent of attosecond metrology using ultrashort and intense lasers has re-triggered strong interest on the topic from an experimental standpoint. Here, we present an approach to measure such emission delays, which does not require attosecond light pulses, and works without the presence of superimposed infrared laser fields. We instead extract the emission delay from the interference pattern generated as the emitted photoelectron is diffracted by the parent ion���s potential. Targeting core electrons in CO, we measured a 2d map of photoelectron emission delays in the molecular frame over a wide range of electron energies. The emission times depend drastically on the photoelectrons��� emission directions in the molecular frame and exhibit characteristic changes along the shape resonance of the molecule., Published by Nature Publishing Group UK, [London]

Double and triple ionisation spectra of the reactive molecule isocyanic acid (HNCO) have been measured using multi-electron and ion coincidence techniques combined with synchrotron radiation and compared with high-level theoretical calculations. Vertical double ionisation at an energy of 32.8 ± 0.3 eV forms the3A” ground state in which the HNCO2+ion is long lived. The vertical triple ionisation energy is determined as 65 ± 1 eV. The core-valence double ionisation spectra resemble the valence photoelectron spectrum in form, and their main features can be understood on the basis of a simple and rather widely applicable Coulomb model based on the characteristics of the molecular orbitals from which electrons are removed. Characteristics of the most important dissociation channels are examined and discussed.

Legendre polynomials form the basis for multipole expansion of spatially varying functions. The technique allows for decomposition of the function into two separate parts with one depending on the radial coordinates only and the other depending on the angular variables. In this work, the angular function $$\cos ^k \theta$$ cos k θ is expanded in the Legendre polynomial basis and the algorithm for determining the corresponding coefficients of the Legendre polynomials is generated. This expansion together with the algorithm can be generalized to any case in which a dot product of any two vectors appears. Two alternative multipole expansions for the electron–electron Coulomb repulsion term are obtained. It is shown that the conventional multipole expansion of the Coulomb repulsion term is a special case for one of the expansions generated in this work.

This work reports on the application of a novel electric field-ionization setup for high-resolution laser spectroscopy measurements on bunched fast atomic beams in a collinear geometry. In combination with multi-step resonant excitation to Rydberg states using pulsed lasers, the field ionization technique demonstrates increased sensitivity for isotope separation and measurement of atomic parameters over previous non-resonant laser ionization methods. The setup was tested at the Collinear Resonance Ionization Spectroscopy experiment at ISOLDE-CERN to perform high-resolution measurements of transitions in the indium atom from the $$\text {5s}^2\text {5d}\,^2\text {D}_{5/2}$$5s25d2D5/2 and $$\text {5s}^2\text {5d}\,^2\text {D}_{3/2}$$5s25d2D3/2 states to $$\text {5s}^2n$$5s2np $$^2$$2P and $$\text {5s}^2n\text {f}\,^2$$5s2nf2F Rydberg states, up to a principal quantum number of $$n=72$$n=72. The extracted Rydberg level energies were used to re-evaluate the ionization potential of the indium atom to be $$46,670.107(4)\,\hbox {cm}^{-1}$$46,670.107(4)cm-1. The nuclear magnetic dipole and nuclear electric quadrupole hyperfine structure constants and level isotope shifts of the $$\text {5s}^2\text {5d}\,^2\text {D}_{5/2}$$5s25d2D5/2 and $$\text {5s}^2\text {5d}\,^2\text {D}_{3/2}$$5s25d2D3/2 states were determined for $$^{113,115}$$113,115In. The results are compared to calculations using relativistic coupled-cluster theory. A good agreement is found with the ionization potential and isotope shifts, while disagreement of hyperfine structure constants indicates an increased importance of electron correlations in these excited atomic states. With the aim of further increasing the detection sensitivity for measurements on exotic isotopes, a systematic study of the field-ionization arrangement implemented in the work was performed at the same time and an improved design was simulated and is presented. The improved design offers increased background suppression independent of the distance from field ionization to ion detection.

Molecular spectroscopy offers opportunities for the exploration of the fundamental laws of nature and the search for new particle physics beyond the standard model1–4. Radioactive molecules—in which one or more of the atoms possesses a radioactive nucleus—can contain heavy and deformed nuclei, offering high sensitivity for investigating parity- and time-reversal-violation effects5,6. Radium monofluoride, RaF, is of particular interest because it is predicted to have an electronic structure appropriate for laser cooling6, thus paving the way for its use in high-precision spectroscopic studies. Furthermore, the effects of symmetry-violating nuclear moments are strongly enhanced5,7–9 in molecules containing octupole-deformed radium isotopes10,11. However, the study of RaF has been impeded by the lack of stable isotopes of radium. Here we present an experimental approach to studying short-lived radioactive molecules, which allows us to measure molecules with lifetimes of just tens of milliseconds. Energetically low-lying electronic states were measured for different isotopically pure RaF molecules using collinear resonance ionisation at the ISOLDE ion-beam facility at CERN. Our results provide evidence of the existence of a suitable laser-cooling scheme for these molecules and represent a key step towards high-precision studies in these systems. Our findings will enable further studies of short-lived radioactive molecules for fundamental physics research., Measurements of low-energy electronic states of radium monofluoride validate predictions of the use of this short-lived radioactive molecule in exploring fundamental physics and provide evidence of its suitability for laser cooling.

L-shell ionisation and subsequent Coulomb explosion of fully deuterated methyl iodide, CD$_3$I, irradiated with hard x-rays has been examined by a time-of-flight multi-ion coincidence technique. The core vacancies relax efficiently by Auger cascades, leading to charge states up to 16+. The dynamics of the Coulomb explosion process are investigated by calculating the ions' flight times numerically based on a geometric model of the experimental apparatus, for comparison with the experimental data. A parametric model of the explosion, previously introduced for multi-photon induced Coulomb explosion, is applied in numerical simulations, giving good agreement with the experimental results for medium charge states. Deviations for higher charges suggest the need to include nuclear motion in a putatively more complete model. Detection efficiency corrections from the simulations are used to determine the true distributions of molecular charge state produced by initial L1, L2 and L3 ionisation., Comment: 6 pages, 4 figures

The recent development of ultrafast extreme ultraviolet (XUV) coherent light sources bears great potential for a better understanding of the structure and dynamics of matter. Promising routes are advanced coherent control and nonlinear spectroscopy schemes in the XUV energy range, yielding unprecedented spatial and temporal resolution. However, their implementation has been hampered by the experimental challenge of generating XUV pulse sequences with precisely controlled timing and phase properties. In particular, direct control and manipulation of the phase of individual pulses within an XUV pulse sequence opens exciting possibilities for coherent control and multidimensional spectroscopy, but has not been accomplished. Here, we overcome these constraints in a highly time-stabilized and phase-modulated XUV-pump, XUV-probe experiment, which directly probes the evolution and dephasing of an inner subshell electronic coherence. This approach, avoiding any XUV optics for direct pulse manipulation, opens up extensive applications of advanced nonlinear optics and spectroscopy at XUV wavelengths., Light pulses with controllable parameters are desired for studying the fundamental properties of matter. Here the authors generate and use phase-manipulated and highly time-stable XUV pulse pairs to probe the coherent evolution and dephasing of XUV electronic coherences in helium and argon.

Previous studies have shown that the cysteine hydropersulfide (Cys-SSH) as the sulfur donor is crucial to sulfur-containing cofactors synthesis. Recently, a selective and sensitive near-infrared ratiometric fluorescent chemosensor Cy-DiSe has been designed and synthesized to detect Cys-SSH spontaneously. Herein, by means of the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) approaches, the sensing mechanism has been thoroughly explored. According to our calculations, the experimental data have been reproduced. The results indicate the intramolecular charge transfer (ICT) is the reason for changes in fluorescence wavelengths. Compared with the chemosensor Cy-DiSe, the larger energy gap of Cy induced by ICT mechanism leads to the blue-shift of the absorption and emission spectra, which guarantees that Cy-DiSe can become a ratiometric fluorescent chemosensor to detect Cys-SSH.

The Kondo effect offers an important paradigm to understand strongly correlated many-body physics. Although under intensive study, some of the important properties of the Kondo effect, in systems where both itinerant coupling and localized coupling play significant roles, are still elusive. Here we report the evolution and universality of the two-stage Kondo effect, the simplest form where both couplings are important using single molecule transistor devices incorporating Manganese phthalocyanine molecules. The Kondo temperature T* of the two-stage Kondo effect evolves linearly against effective interaction of involved two spins. Observed Kondo resonance shows universal quadratic dependence with all adjustable parameters: temperature, magnetic field and biased voltages. The difference in nonequilibrium conductance of two-stage Kondo effect to spin 1/2 Kondo effect is also identified. Messages learned in this study fill in directive experimental evidence of the evolution of two-stage Kondo resonance near a quantum phase transition point, and help in understanding sophisticated molecular electron spectroscopy in a strong correlation regime., The Kondo effect can serve as a powerful paradigm to understand strongly correlated many-body processes in physics. Here, Guo et al. utilize single molecule transistor devices as a testbed to study multi-level Kondo correlation and show electrical gate evolution and the universality of the two-stage Kondo effect.

Recent theoretical works have proposed atomic clocks based on narrow optical transitions in highly charged ions. The most interesting candidates for searches of physics beyond the Standard Model are those which occur at rare orbital crossings where the shell structure of the periodic table is reordered. There are only three such crossings expected to be accessible in highly charged ions, and hitherto none have been observed as both experiment and theory have proven difficult. In this work we observe an orbital crossing in a system chosen to be tractable from both sides: Pr\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${}^{9+}$$\end{document}9+. We present electron beam ion trap measurements of its spectra, including the inter-configuration lines that reveal the sought-after crossing. With state-of-the-art calculations we show that the proposed nHz-wide clock line has a very high sensitivity to variation of the fine-structure constant, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\alpha$$\end{document}α, and violation of local Lorentz invariance; and has extremely low sensitivity to external perturbations., Atomic clocks are based on the frequency of optical transitions and offer high precision. Here the authors demonstrate a configuration crossing in the highly charged ion praseodymium (Pr\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${}^{9+}$$\end{document}9+) and determine the frequency of a potential reference transition for a highly charged ion clock.

Intramolecular charge transfer processes play an important role in many biological, chemical and physical processes including photosynthesis, redox chemical reactions and electron transfer in molecular electronics. These charge transfer processes are frequently influenced by the dynamics of their molecular or atomic environments, and they are accompanied with energy dissipation into this environment. The detailed understanding of such processes is fundamental for their control and possible exploitation in future technological applications. Most of the experimental studies of the intramolecular charge transfer processes so far have been carried out using time-resolved optical spectroscopies on large molecular ensembles. This hampers detailed understanding of the charge transfer on the single molecular level. Here we build upon the recent progress in scanning probe microscopy, and demonstrate the control of mixed valence state. We report observation of single electron transfer between two ferrocene redox centers within a single molecule and the detection of energy dissipation associated with the single electron transfer., Here, the authors use atomic force microscopy under ultra-high vacuum conditions to study intramolecular single electron transfer within a single molecule. This allows them to investigate energy dissipation process related to the electron transfer as a function of temperature.

Attosecond probing of core-level electronic transitions provides a sensitive tool for studying valence molecular dynamics with atomic, state, and charge specificity. In this report, we employ attosecond transient absorption spectroscopy to follow the valence dynamics of strong-field initiated processes in methyl bromide. By probing the 3d core-to-valence transition, we resolve the strong field excitation and ensuing fragmentation of the neutral σ* excited states of methyl bromide. The results provide a clear signature of the non-adiabatic passage of the excited state wavepacket through a conical intersection. We additionally observe competing, strong field initiated processes arising in both the ground state and ionized molecule corresponding to vibrational and spin-orbit motion, respectively. The demonstrated ability to resolve simultaneous dynamics with few-femtosecond resolution presents a clear path forward in the implementation of attosecond XUV spectroscopy as a general tool for probing competing and complex molecular phenomena with unmatched temporal resolution., Excited-state molecular dynamics may be too complex to be resolved by femtosecond spectroscopic studies. Here the authors resolve the competing pathways in the excited state dynamics of methyl bromide by attosecond transient absorption spectroscopy, from excitation to fragmentation.

We present a detailed study to resolve the discrepancy between the existing theoretically estimated oscillator strengths and the recently observed result from the X-ray free electron laser (XFEL) experiment performed at the Linac Coherent Light Source (LCLS) for the intensity ratio between two of the strongest emission lines from Ne-like Fe XVII (Fe16+) ion. By including the dynamic resonance induced population transfer due to autoionization between the coexisting Fe XVII and Fe XVI (Fe15+) ions in the XFEL experiment, we are able to successfully resolve this difference in theory and experiment. Further experimental works are suggested for a more detailed understanding of the dynamic resonance processes for ions.

We present experimental results on the characteristic sharing of available excess energy, ranging from 11–221 eV, between two electrons in single-photon direct double ionization of He. An effective parametrization of the sharing distributions is presented along with an empirical model that describes the complete shape of the distribution based on a single experimentally determinable parameter. The measured total energy sharing distributions are separated into two distributions representing the shake-off and knock-out parts by simulating the sharing distribution curves expected from a pure wave collapse after a sudden removal of the primary electron. In this way, empirical knock-out distributions are extracted and both the shake-off and knock-out distributions are parametrized. These results suggest a simple method that can be applied to other atomic and molecular systems to experimentally study important aspects of the direct double ionization process.

We report a measurement of the lifetime of the cesium 7s 2S1/2 state using time-correlated single-photon counting spectroscopy in a vapor cell. We excite the atoms using a Doppler-free two-photon transition from the 6s 2S1/2 ground state, and detect the 1.47-μm photons from the spontaneous decay of the 7s 2S1/2 to the 6p 2P3/2 state. We use a gated single-photon detector in an asynchronous mode, allowing us to capture the fluorescence profile for a window much larger than the detector gate length. Analysis of the exponential decay of the photon count yields a 7s 2S1/2 lifetime of 48.28 ± 0.07 ns, an uncertainty of 0.14%. These measurements provide sensitive tests of theoretical models of the Cs atom, which play a central role in parity violation measurements.

Theoretical studies of lattice- and spin-polarons are presented in this thesis, where the primary tool is ab-initio electronic structure calculations. The studies are performed with employment of a variety of analytical and computational methods. For lattice-polarons, we present an analytical study where multipolaron solutions were found in the framework of the Holstein 1D molecular crystal model. Interestingly, we found a new periodic, dnoidal, solution for the multipolaron system. In addition to it, we examined the stability of multipolaron solutions, and it was found that cnoidal and dnoidal solutions stabilize in different ranges of the parameter space. Moreover, we add to the model nonlocal effects and described dynamics in terms of internal solitonic modes. Hole-polaron localization accompanying the formation of a cation vacancy in bulk MgO and CaO and at the (100) MgO/CaO interfaces is presented. We show that the ground state is found to be the O1-O1 bipolaronic configuration both in bulk oxides and at their interfaces. Moreover, the one-centered O2-O0 bipolaron was found to be metastable with its stability being enhanced at the interfaces compared to that in bulk oxides. Also, for several bipolaronic configurations, we analyzed possible transitions from O1-O1 to O2-O0. On the same line of reasoning, electron localization and polaron mobility in oxygen-deficient and Li-doped monoclinic tungsten trioxide has been studied. It is shown for WO3, that small polarons formed in the presence of oxygen vacancy prefer bipolaronic W5+-W5+ configuration rather than W6+-W4+ configuration, which is found to be metastable state. Also, it is demonstrated that the bipolarons are tightly bound to vacancies, and consequently exhibit low mobility in the crystal. On the other hand, we show that polarons formed as a result of Li intercalation are mobile and that they are being responsible for electrochromic properties discovered in the compound. Spin-polaron formation in La-doped CaMnO3, with G-type antiferromagnetic structure, was also studied. We found that for this material, spin-polarons are stabilized due to the interplay of magnetic and lattice-effects at lower La concentrations and mostly due to the lattice contribution at larger concentrations. We show that the formation of SP is unfavourable in the C- and A-type antiferromagnetic phase, in agreement with previously reported experimental studies. We have also studied dynamical and temperature dependent properties of spin-polarons in this compound. We estimated material specific exchange parameters from density functional theory and found that 3D magnetic polarons in the Heisenberg lattice stabilize at slightly higher temperatures than in the case of 2D magnetic polarons. Next, we have proposed a method to calculate magnetic polaron hopping barriers and studied spin-polaron mobility CaMnO3 using additional methods such as atomistic spin dynamics and kinetic Monte Carlo. We make a suggestion of using this system in nano-technological applications.

The recently theoretically described nuclear spin-induced circular dichroism (NSCD) is a promising method for the optical detection of nuclear magnetization. NSCD involves both optical excitations of the molecule and hyperfine interactions and, thus, it offers a means to realize a spectroscopy with spatially localized, high-resolution information. To survey the factors relating the molecular and electronic structure to the NSCD signal, we theoretically investigate NSCD of twenty structures of the four most common nucleic acid bases (adenine, guanine, thymine, cytosine). The NSCD signal correlates with the spatial distribution of the excited states and couplings between them, reflecting changes in molecular structure and conformation. This constitutes a marked difference to the nuclear magnetic resonance (NMR) chemical shift, which only reflects the local molecular structure in the ground electronic state. The calculated NSCD spectra are rationalized by means of changes in the electronic density and by a sum-over-states approach, which allows to identify the contributions of the individual excited states. Two separate contributions to NSCD are identified and their physical origins and relative magnitudes are discussed. The results underline NSCD spectroscopy as a plausible tool with a power for the identification of not only different molecules, but their specific structures as well.

The authors have synthesized fergusonite-structured La(Nb0·71V0·04Mn0·25)O4 samples. The samples, consisting of La3+, Nb5+, V5+, Mn4+ and oxygen ions, demonstrated temperature-dependent magnetization that increased with lowering the temperature below ≈200 K, and almost saturated below ≈100 K. At 75 K, the field-dependent magnetization demonstrated sigmoidal curve and reached 3 μB/Mn at 1 T. Such a magnetic behavior can be ascribed to exchange interaction between Mn4+Nb2O11 nanoclusters. The Mn4+ substitution for the V5+ sites of the crystal resulted also in the occupied state above the valence band maximum.

In non-resonant Auger electron spectroscopies, multi core-ionized states lead to numerous energetically close-lying electronic transitions in Auger spectra, this hampering the assignment and interpretation of the experimental results. Here we reveal a new method to overcome this intrinsic limitation of non-resonant inner-shell spectroscopies. In a proof-of-principle experiment performed for the O₂ molecule, most of the Auger final states are dissociative, and we measure in coincidence the kinetic energy of the photoelectron and the kinetic energy release of the (O⁺, O⁺) ion pairs produced after the Auger decay of the O 1s−1 core-ionized states. The Auger final states are assigned using energy conservation. We fully separate the contributions from the ⁴Σ− and ²Σ− intermediate ionic states and conclusively demonstrate that the Auger decay probability can dramatically depend on the different O₂ 1s−1 intermediate multiplet states. In addition, a metastable Auger final state also exists, with lifetime longer than 3.8 μs, and clear changes are observed in both branching ratio and spectral profile of the O 1s photoelectron spectrum when they are recorded in coincidence with either O₂⁺⁺ or with other ionic species. These changes are attributed to the population of the metastable B′³Σ−u(ν′′=0) Auger final state via different intermediate states.

Recent advances in X-ray instrumentation have made it possible to measure the spectra of an essentially unexplored class of electronic states associated with double inner-shell vacancies. Using the technique of single electron spectroscopy, spectra of states in CS2 and SF6 with a double hole in the K-shell and one electron exited to a normally unoccupied orbital have been obtained. The spectra are interpreted with the aid of a high-level theoretical model giving excellent agreement with the experiment. The results shed new light on the important distinction between direct and conjugate shake-up in a molecular context. In particular, systematic similarities and differences between pre-edge states near single core holes investigated in X-ray absorption spectra and the corresponding states near double core holes studied here are brought out.

We present a structural data set of the 20 proteinogenic amino acids and their amino-methylated and acetylated (capped) dipeptides. Different protonation states of the backbone (uncharged and zwitterionic) were considered for the amino acids as well as varied side chain protonation states. Furthermore, we studied amino acids and dipeptides in complex with divalent cations (Ca2+, Ba2+, Sr2+, Cd2+, Pb2+, and Hg2+). The database covers the conformational hierarchies of 280 systems in a wide relative energy range of up to 4 eV (390 kJ/mol), summing up to an overall of 45,892 stationary points on the respective potential-energy surfaces. All systems were calculated on equal first-principles footing, applying density-functional theory in the generalized gradient approximation corrected for long-range van der Waals interactions. We show good agreement to available experimental data for gas-phase ion affinities. Our curated data can be utilized, for example, for a wide comparison across chemical space of the building blocks of life, for the parametrization of protein force fields, and for the calculation of reference spectra for biophysical applications., The reported data can be accessed in the NOMAD repository via the link http://dx.doi.org/10.17172/NOMAD/20150526220502 or on this website: http://aminoaciddb.rz-berlin.mpg.de

The present review provides comprehensive information on finite nuclear charge density distribution models, not only for the purpose of quantum chemical electronic structure calculations for atoms and molecules, but also for other fields of atomic and molecular physics, A general discussion of the electrostatic behaviour of nuclear charge density distributions, spherical ones and non-spherical ones, is given. A large and reasonably complete set of spherical finite nucleus models, covering all models widely used in atomic and nuclear physics, is discussed in detail. Analytic expressions are given for charge density distributions, for important radial expectation values, and for their corresponding electrostatic potentials; these include new material not found in the literature. Thus, the necessary prerequisites for the use of finite nucleus models which are more realistic than the simple, frequently considered models (e.g., the 'homogeneous', 'Gaussian', and Fermi models) are fulfilled. The use of finite nucleus models in standard quantum chemical electronic structure programs is briefly reviewed. In order to detect differences between physical properties obtained with various finite nucleus models. six standardized models were selected to study and compare energy shifts (non-relativistic and relativistic) in hydrogen-like atoms. It is shown that within this set a clear differentiation of models can be made, not only from the point of View of total energy shifts but also from the point of view of energy differences and in fact even for rather low nuclear charge numbers. This could be important for future experimental as well as theoretical work on hydrogen-like atoms. (C) 2000 Elsevier Science B.V. All rights reserved.

Laser-induced grating spectroscopy (LIGS) is for the first time explored in a configuration based on the crossing of two focused femtosecond (fs) laser pulses (800-nm wavelength) and a focused continuous-wave (cw) laser beam (532-nm wavelength). A thermal grating was formed by multi-photon absorption of the fs-laser pulses by $$\hbox {N}_{{2}}$$ N 2 with a pulse energy around 700 $$\upmu $$ μ J ($$\sim $$ ∼ 45 TW/$$\hbox {cm}^{2}$$ cm 2 ). The feasibility of this LIGS configuration was investigated for thermometry in heated nitrogen gas flows. The temperature was varied from room temperature up to 750 K, producing strong single-shot LIGS signals. A model based on the solution of the linearized hydrodynamic equations was used to extract temperature information from single-shot experimental data, and the results show excellent agreement with the thermocouple measurements. Furthermore, the fluorescence produced by the fs-laser pulses was investigated. This study indicates an 8-photon absorption pathway for $$\hbox {N}_{{2}}$$ N 2 in order to reach the $$\hbox {B}^{3}\Pi _{g}$$ B 3 Π g state from the ground state, and 8 + 5 photon excitation to reach the $$\hbox {B}^{2}\Sigma _{u}^{+}$$ B 2 Σ u + state of the $$\hbox {N}_{2}^{+}$$ N 2 + ion. At pulse energies higher than 1 mJ, the LIGS signal was disturbed due to the generation of plasma. Additionally, measurements in argon gas and air were performed, where the LIGS signal for argon shows lower intensity compared to air and $$\hbox {N}_{{2}}$$ N 2 .