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1.
J Phys Chem A ; 2019 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-31386367

RESUMO

We demonstrate that the possibility of monitoring relative photoionization cross sections over a large photon energy range allows us to study and disentangle shake processes and intramolecular inelastic scattering effects. In this gas-phase study, relative intensities of the carbon 1s photoelectron lines from chemically inequivalent carbon atoms in the same molecule have been measured as a function of the incident photon energy in the range of 300-6000 eV. We present relative cross sections for the chemically shifted carbon 1s lines in the photoelectron spectra of ethyl trifluoroacetate (the "ESCA" molecule). The results are compared with those of methyl trifluoroacetate and S-ethyl trifluorothioacetate as well as a series of chloro-substituted ethanes and 2-butyne. In the soft X-ray energy range, the cross sections show an extended X-ray absorption fine structure type of wiggles, as was previously observed for a series of chloroethanes. The oscillations are damped in the hard X-ray energy range, but deviations of cross-section ratios from stoichiometry persist, even at high energies. The current findings are supported by theoretical calculations based on a multiple scattering model. The use of soft and tender X-rays provides a more complete picture of the dominant processes accompanying photoionization. Such processes reduce the main photoelectron line intensities by 20-60%. Using both energy ranges enabled us to discern the process of intramolecular inelastic scattering of the outgoing electron, whose significance is otherwise difficult to assess for isolated molecules. This effect relates to the notion of the inelastic mean free path commonly used in photoemission studies of clusters and condensed matter.

2.
Phys Chem Chem Phys ; 21(17): 8827-8836, 2019 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-30972388

RESUMO

The Si 1s-1, Si 2s-1, and Si 2p-1 photoelectron spectra of the SiX4 molecules with X = F, Cl, Br, CH3 were measured. From these spectra the Si 1s-1 and Si 2s-1 lifetime broadenings were determined, revealing a significantly larger value for the Si 2s-1 core hole of SiF4 than for the same core hole of the other molecules of the sequence. This finding is in line with the results of the Si 2p-1 core holes of a number of SiX4 molecules, with an exceptionally large broadening for SiF4. For the Si 2s-1 core hole of SiF4 the difference to the other SiX4 molecules can be explained in terms of Interatomic Coulomb Decay (ICD)-like processes. For the Si 2p-1 core hole of SiF4 the estimated values for the sum of the Intraatomic Auger Electron Decay (IAED) and ICD-like processes are too small to explain the observed linewidth. However, the results of the given discussion render for SiF4 significant contributions from Electron Transfer Mediated Decay (ETMD)-like processes at least plausible. On the grounds of our results, some more molecular systems in which similar processes can be observed are identified.

3.
Proc Natl Acad Sci U S A ; 116(11): 4877-4882, 2019 03 12.
Artigo em Inglês | MEDLINE | ID: mdl-30733297

RESUMO

Observing and controlling molecular motion and in particular rotation are fundamental topics in physics and chemistry. To initiate ultrafast rotation, one needs a way to transfer a large angular momentum to the molecule. As a showcase, this was performed by hard X-ray C1s ionization of carbon monoxide accompanied by spinning up the molecule via the recoil "kick" of the emitted fast photoelectron. To visualize this molecular motion, we use the dynamical rotational Doppler effect and an X-ray "pump-probe" device offered by nature itself: the recoil-induced ultrafast rotation is probed by subsequent Auger electron emission. The time information in our experiment originates from the natural delay between the C1s photoionization initiating the rotation and the ejection of the Auger electron. From a more general point of view, time-resolved measurements can be performed in two ways: either to vary the "delay" time as in conventional time-resolved pump-probe spectroscopy and use the dynamics given by the system, or to keep constant delay time and manipulate the dynamics. Since in our experiment we cannot change the delay time given by the core-hole lifetime τ, we use the second option and control the rotational speed by changing the kinetic energy of the photoelectron. The recoil-induced rotational dynamics controlled in such a way is observed as a photon energy-dependent asymmetry of the Auger line shape, in full agreement with theory. This asymmetry is explained by a significant change of the molecular orientation during the core-hole lifetime, which is comparable with the rotational period.

4.
J Phys Chem Lett ; 9(15): 4457-4462, 2018 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-30020787

RESUMO

X-ray absorption and Auger electron spectroscopies are demonstrated to be powerful tools to unravel the electronic structure of solvated ions. In this work for the first time, we use a combination of these methods in the tender X-ray regime. This allowed us to address electronic transitions from deep core levels, to probe environmental effects, specifically in the bulk of the solution since the created energetic Auger electrons possess large mean free paths, and moreover, to obtain dynamical information about the ultrafast delocalization of the core-excited electron. In the considered exemplary aqueous KCl solution, the solvated isoelectronic K+ and Cl- ions exhibit notably different Auger electron spectra as a function of the photon energy. Differences appear due to dipole-forbidden transitions in aqueous K+ whose occurrence, according to the performed ab initio calculations, becomes possible only in the presence of solvent water molecules.

5.
ACS Appl Mater Interfaces ; 10(9): 8132-8140, 2018 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-29411962

RESUMO

Vertical crossbar devices based on manganite and cobalt injecting electrodes and a metal-quinoline molecular transport layer are known to manifest both magnetoresistance (MR) and electrical bistability. The two effects are strongly interwoven, inspiring new device applications such as electrical control of the MR and magnetic modulation of bistability. To explain the device functionality, we identify the mechanism responsible for electrical switching by associating the electrical conductivity and the impedance behavior with the chemical states of buried layers obtained by in operando photoelectron spectroscopy. These measurements revealed that a significant fraction of oxygen ions migrate under voltage application, resulting in a modification of the electronic properties of the organic material and of the oxidation state of the interfacial layer with the ferromagnetic contacts. Variable oxygen doping of the organic molecules represents the key element for correlating bistability and MR, and our measurements provide the first experimental evidence in favor of the impurity-driven model describing the spin transport in organic semiconductors in similar devices.

6.
ACS Appl Mater Interfaces ; 9(27): 23099-23106, 2017 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-28613812

RESUMO

We report the study of anatase TiO2(001)-oriented thin films grown by pulsed laser deposition on LaAlO3(001). A combination of in situ and ex situ methods has been used to address both the origin of the Ti3+-localized states and their relationship with the structural and electronic properties on the surface and the subsurface. Localized in-gap states are analyzed using resonant X-ray photoelectron spectroscopy and are related to the Ti3+ electronic configuration, homogeneously distributed over the entire film thickness. We find that an increase in the oxygen pressure corresponds to an increase in Ti3+ only in a well-defined range of deposition pressure; outside this range, Ti3+ and the strength of the in-gap states are reduced.

7.
J Phys Chem Lett ; 8(12): 2730-2734, 2017 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-28562043

RESUMO

Near-zone Förster resonant energy transfer is the main effect responsible for excitation energy flow in the optical region and is frequently used to obtain structural information. In the hard X-ray region, the Förster law is inadequate because the wavelength is generally shorter than the distance between donors and acceptors; hence, far-zone resonant energy transfer (FZRET) becomes dominant. We demonstrate the characteristics of X-ray FZRET and its fundamental differences with the ordinary near-zone resonant energy-transfer process in the optical region by recording and analyzing two qualitatively different systems: high-density CuO polycrystalline powder and SF6 diluted gas. We suggest a method to estimate geometrical structure using X-ray FZRET employing as a ruler the distance-dependent shift of the acceptor core ionization potential induced by the Coulomb field of the core-ionized donor.

8.
Phys Rev Lett ; 116(21): 213001, 2016 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-27284654

RESUMO

Creation of deep core holes with very short (τ≤1 fs) lifetimes triggers a chain of relaxation events leading to extensive nuclear dynamics on a few-femtosecond time scale. Here we demonstrate a general multistep ultrafast dissociation on an example of HCl following Cl 1s→σ^{*} excitation. Intermediate states with one or multiple holes in the shallower core electron shells are generated in the course of the decay cascades. The repulsive character and large gradients of the potential energy surfaces of these intermediates enable ultrafast fragmentation after the absorption of a hard x-ray photon.

9.
Phys Chem Chem Phys ; 18(22): 15133-42, 2016 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-27199185

RESUMO

We have measured resonant-Auger decay following Cl 1s(-1) excitations in HCl and CH3Cl molecules, and extracted the pseudo-cross sections of different Cl 2p(-2) final states. These cross sections show clear evidence of shake processes as well as contributions of electronic state-lifetime interference (ELI). To describe the spectra we developed a fit approach that takes into account ELI contributions and ultrafast nuclear dynamics in dissociative core-excited states. Using this approach we utilized the ELI contributions to obtain the intensity ratios of the overlapping states Cl 1s(-1)4pπ/1s(-1)4pσ in HCl and Cl 1s(-1)4pe/1s(-1)4pa1 in CH3Cl. The experimental value for HCl is compared with theoretical results showing satisfactory agreement.

10.
Phys Rev Lett ; 114(9): 093001, 2015 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-25793809

RESUMO

Direct measurements of Ar^{+} 1s^{-1}2p^{-1}nl double-core-hole shake-up states are reported using conventional single-channel photoemission, offering a new and relatively easy means to study such species. The high-quality results yield accurate energies and lifetimes of the double-core-hole states. Their photoemission spectrum also can be likened to 1s absorption of an exotic argon ion with a 2p core vacancy, providing new information about the spectroscopy of both this unusual ionic state as well as the neutral atom.

11.
J Chem Phys ; 141(14): 144301, 2014 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-25318716

RESUMO

We report a theoretical and experimental study of the high resolution resonant K(α) X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K(α) emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

12.
Nat Commun ; 5: 4069, 2014 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-24906107

RESUMO

Studies of photoemission processes induced by hard X-rays including production of energetic electrons have become feasible due to recent substantial improvement of instrumentation. Novel dynamical phenomena have become possible to investigate in this new regime. Here we show a significant change in Auger emission following 1s photoionization of neon, which we attribute to the recoil of the Ne ion induced by the emission of a fast photoelectron. Because of the preferential motion of the ionized Ne atoms along two opposite directions, an Auger Doppler shift is revealed, which manifests itself as a gradual broadening and doubling of the Auger spectral features. This Auger Doppler effect should be a general phenomenon in high-energy photoemission of both isolated atoms and molecules, which will have to be taken into account in studies of other recoil effects such as vibrational or rotational recoil in molecules, and may also have consequences in measurements in solids.

13.
Phys Chem Chem Phys ; 15(44): 19322-9, 2013 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-24121279

RESUMO

The angular anisotropy of fragments created in the dissociation of core-electron excited water molecules is studied to probe the correlation between fragmentation channels, kinematics and molecular geometry. We present fragment kinetic measurements for water molecules where the inner-shell oxygen electron is excited to the unoccupied 4a1 and 2b2 valence molecular orbitals. The kinematics of individual fragmentation channels are measured using fully three-dimensional momentum imaging of fragments. The results show that the geometry of the molecule and the kinetic energy of fragments are strongly coupled in the atomisation process. In addition we identify a fragmentation process arising from bond rearrangement evidenced by the H2(+)-O(+) ion pair which is accessible for resonant excitation of the 1s electron. In all of the two-body fragmentation processes the dissociation takes place along the potential-energy surface, while atomisation reveals both dissociation along the potential surface and Coulomb explosion. The angular distribution of fragments suggests that the bond rearrangement is very rapid; likely on a sub 10 fs time scale.


Assuntos
Água/química , Elétrons , Íons , Cinética , Modelos Moleculares
14.
Phys Chem Chem Phys ; 11(5): 826-33, 2009 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-19290329

RESUMO

In this study linear free energy relationships (LFER) are applied to the relaxation of core-excited states in aliphatic CH(3)X compounds. There are at least two valence orbitals involved in Auger decay following C(CH(3))1s -->sigma*(C-X) excitation, which may as well be localized on the substituents in this series. Therefore, the observed property cannot be strictly attached to the so-called reaction center. The behavior of substituent constants in the description of core-hole processes in aliphatic compounds is also checked on C1s ionization potentials for the extended series of substituted methanes. The role of the inductive effect for both resonant Auger kinetic energies (E(k)) and C1s binding energies (E) is very important. C(CH(3))1s -->sigma*(C-X) excitation energies do not show any significant correlations with inductive substituent constants. On the contrary, Taft's inductive parameters alone give good correlations for E(k). A simple model with 'Z + 1' approximation is developed to describe E(k) and explain the observed correlations: [formula: see text] where E(b)(v(Z)) is the valence ionization potential for CH(3)X and E(ea(Z+1)(+)) is the electron affinity for [NH(3)X](+).

15.
J Chem Phys ; 128(15): 154314, 2008 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-18433216

RESUMO

Core excitation triggers nuclear dynamics on the femtosecond time scale. A multiparametric electron/ion coincidence approach has been used to disentangle complex decay processes occurring at short (molecular) or long (atomic) time scales. Methyl chloride has been excited by scanning along the dissociative Cl2p-->sigma* resonance. The detailed chronology of the competing decay processes, leading to either the rearrangement product HCl(+), or an ultrafast dissociation leading to Cl(+), has been investigated. The observed Auger-Doppler shift has been analyzed for various orientations of the electron and fragment ion.

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