Resonant Auger Electron Spectroscopy Research Articles

Rebuilding the vibrational wavepacket in TRAS using attosecond X-ray pulses

Time-resolved X-ray photoelectron spectroscopy (TXPS) is a well-established technique to probe coherent nuclear wavepacket dynamics using both table-top and free-electron-based ultrafast X-ray lasers. Energy resolution, however, becomes compromised for a very short pulse duration in the sub-femtosecond range. By resonantly tuning the X-ray pulse to core-excited states undergoing Auger decay, this drawback of TXPS can be mitigated. While resonant Auger-electron spectroscopy (RAS) can recover the vibrational structures not hidden by broadband excitation, the full reconstruction of the wavepacket is a standing challenge. Here, we theoretically demonstrate how the complete information of a nuclear wavepacket, i.e., the populations and relative phases of the vibrational states constituting the wavepacket, can be retrieved from time-resolved RAS (TRAS) measurements. Thus, TRAS offers key insights into coupled nuclear and electronic dynamics in complex systems on ultrashort timescales, providing an alternative to leverage femtosecond and attosecond X-ray probe pulses.

Experimental and theoretical investigation of the Auger electron spectra of isothiocyanic acid, HNCS.

We investigate isothiocyanic acid, HNCS, by resonant and nonresonant Auger electron spectroscopy at the K-edge of carbon and nitrogen, and the L2,3-edge of sulfur, employing soft X-ray synchrotron radiation. The C1s and N1s ionization energies as well as the S2s and S2p ionization energies are determined and X-ray absorption spectra reveal the transitions from the core to the virtual orbitals. Final states for all normal Auger electron spectra and the resonant ones recorded at the carbon and nitrogen edge are assigned and rationalized with theoretical spectra obtained with a wave-function based protocol. The latter is based on ab initio configuration-interaction representations of the bound part of the electronic wave functions, the one-center approximation for Auger intensities, and a moment theory for band shapes. The computed spectra are in very good agreement with the experimental data and most of the relevant signals are assigned. The double ionization energy is derived from the S2p1/2 spectrum and in good agreement with a recently determined value. The Auger electron spectra are compared with those of the congener HNCO. A similar shape of the normal Auger electron spectra was found for the low binding energy final states, while intensities differed. Similarities are less pronounced in the resonant Auger electron spectra.

Electronic coupling between the unoccupied states of the organic and inorganic sublattices of methylammonium lead iodide: A hybrid organic-inorganic perovskite single crystal

Organic-inorganic halide perovskites have been intensively re-investigated due to their applications, yet the opto-electronic function of the organic cation remains unclear. Through organic-selective resonant Auger electron spectroscopy measurements on well-defined single crystal surfaces, we find evidence for electronic coupling in the unoccupied states between the organic and inorganic sub-lattices of the prototypical hybrid perovskite, which is contrary to the notion based on previous studies that the organic cation is electronically inert. The coupling is relevant for electron dynamics in the material and for understanding opto-electronic functionality.

Femtosecond Charge Transfer Dynamics in Monomolecular Films in the Context of Molecular Electronics.

A key issue of molecular electronics (ME) is the correlation between the molecular structure and the charge transport properties of the molecular framework. Accordingly, a variety of model and potentially useful molecular systems are designed, to prove a particular function or correlation or to build a prototype device. These studies usually involve the measurements of the static electric conductance properties of individual molecules and their assembles on solid supports. At the same time, information about the dynamics of the charge transport (CT) and transfer in such systems, complementary in the context of ME and of a scientific value on its own, is quite scarce. Among other means, this drawback can be resolved by resonant Auger electron spectroscopy (RAES) in combination with core hole clock (CHC) approach, as described in this Account. The RAES-CHC scheme was applied to a variety of aliphatic and aromatic self-assembled monolayers (SAMs), adsorbed on Au(111) over the thiolate and selenolate docking groups. Electron transfer (ET) from a suitable terminal tail group to the substrate, across the molecular framework, was monitored, triggered by resonant excitation of this group (nitrile in most cases) by narrow-band X-ray radiation. This resulted in the quantitative data for the characteristic ET time, τET, in the femtosecond domain, with the time window ranging from ∼1 fs to ∼120 fs. The derived τET exhibit an exponential dependence on the molecular length, mimicking the behavior of the static conductance and suggesting a common physical basis behind the static CT and ET dynamics. The dynamic decay factors, βET, for the alkyl, oligophenyl, and acene molecular "wires" correlate well with the analogous parameters for the static CT. Both τET and βET values exhibit a distinct dependence on the character of the involved molecular orbital (MO), demonstrating that the efficiency and rate of the CT in molecular assemblies can be controlled by resonant injection of the charge carriers into specific MOs. This dependence as well as a lack of correlation between the molecular tilt and τET represent strong arguments in favor of the generally accepted model of CT across the molecular framework ("through-bond") in contrast to "through-space" tunneling. Comparison of the SAMs with thiolate and selenolate docking groups suggests that the use of selenolate instead of thiolate does not give any gain in terms of ET dynamics or molecular conductance. Whereas a certain difference in the efficiency of the electronic coupling of thiolate and selenolate to the substrate cannot be completely excluded, this difference is certainly too small to affect the performance of the entire molecule to a noticeable extent. The efficient electronic coupling of the thiolate docking group to the substrate was verified and the decoupling of the electronic subsystems of the substrate and π-conjugated segment by introduction of methylene group into the backbone was demonstrated. No correlation between the molecular dipole or fluorine substitution pattern (at the side positions) and the ET efficiency was recorded. Several representative examples for the resonantly addressable tail groups are given, and perspectives for future research in the context of ET dynamics in molecular assemblies are discussed.

Electron Transfer Dynamics and Structural Effects in Benzonitrile Monolayers with Tuned Dipole Moments by Differently Positioned Fluorine Atoms.

To understand the influence of the molecular dipole moment on the electron transfer (ET) dynamics across the molecular framework, two series of differently fluorinated, benzonitrile-based self-assembled monolayers (SAMs) bound to Au(111) by either thiolate or selenolate anchoring groups were investigated. Within each series, the molecular structures were the same with the exception of the positions of two fluorine atoms affecting the dipole moment of the SAM-forming molecules. The SAMs exhibited a homogeneous anchoring to the substrate, nearly upright molecular orientations, and the outer interface comprised of the terminal nitrile groups. The ET dynamics was studied by resonant Auger electron spectroscopy in the framework of the core-hole clock method. Resonance excitation of the nitrile group unequivocally ensured an ET pathway from the tail group to the substrate. As only one of the π* orbitals of this group is hybridized with the π* system of the adjacent phenyl ring, two different ET times could be determined depending on the primary excited orbital being either localized at the nitrile group or delocalized over the entire benzonitrile moiety. The latter pathway turned out to be much more efficient, with the characteristic ET times being a factor 2.5-3 shorter than those for the localized orbital. The dynamic ET properties of the analogous thiolate- and selenolate-based adsorbates were found to be nearly identical. Finally and most importantly, these properties were found to be unaffected by the different patterns of the fluorine substitution used in the present study, thus showing no influence of the molecular dipole moment.

Core hole processes in x-ray absorption and photoemission by resonant Auger-electron spectroscopy and first-principles theory.

Electron-core hole interactions are critical for proper interpretation of core-level spectroscopies commonly used as analytical tools in materials science. Here we utilize resonant Auger-electron spectroscopy to uniquely identify exciton, shake, and charge-transfer processes that result from the sudden creation of the core hole in both x-ray-absorption and photoemission spectra. These effects are captured for the transition-metal compounds SrTiO3 and MoS2 by fully ab initio, combined real-time cumulant, and Bethe-Salpeter equation approaches to account for core hole dynamics and screening. Atomic charges and excited-state electron-density fluctuations reflect materials' solid-state electronic structure, loss of translational symmetry around the core hole, and breakdown of the sudden approximation. They also demonstrate competition between long- and short-range screening in a solid.

Ultrafast core-excited electron dynamics in model crystalline organic semiconductors.

Electron transfer is key to the operation of devices based on molecular (organic) semiconductors. Others have shown that electron transfer in the solid state often proceeds on sub-50 fs timescales, the details of which can be difficult to temporally resolve using pump-probe spectroscopy. A popular technique to measure average time scales for such rapid electron-transfer events is the core-hole clock implementation of resonant Auger electron spectroscopy at a single X-ray absorption edge. This is often done on relatively small molecules with core-excited states that are highly localized. We have used resonant Auger spectroscopy to probe sub-50 fs electron dynamics of two relatively large model organic semiconductors: Cu phthalocyanine (CuPc) along with its fluorinated analog, F16CuPc. We have interrogated electron dynamics simultaneously at N and C K-edges, along with calculations of initial and final states participating in the core-excited states. Our measurements show that the electron dynamics differ substantially across the two absorption edges for a given molecule, and that there are significant differences at a given edge between the two derivatives. X-ray spectroscopy calculations suggest that the extension of π-electron density onto peripheral F atoms in F16CuPc is implicated in the large change in ultrafast electron dynamics upon fluorination. We believe our results have important implications for analysis of core-hole clock measurements on relatively large organic semiconductors.

Core Shell Investigation of 2-nitroimidazole.

Tunability and selectivity of synchrotron radiation have been used to study the excitation and ionization of 2-nitroimidazole at the C, N, and O K-edges. The combination of a set of different measurements (X-ray photoelectron spectroscopy, near-edge photoabsorption spectroscopy, Resonant Auger electron spectroscopy, and mass spectrometry) and computational modeling have successfully disclosed local effects due to the chemical environment on both excitation/ionization and fragmentation of the molecule.

Electron spectroscopy of ionic liquids: experimental identification of atomic orbital contributions to valence electronic structure.

The atomic contributions to valence electronic structure for 37 ionic liquids (ILs) are identified using a combination of variable photon energy XPS, resonant Auger electron spectroscopy (RAES) and a subtraction method. The ILs studied include a diverse range of cationic and anionic structural moieties. We introduce a new parameter for ILs, the energy difference between the energies of the cationic and anionic highest occupied fragment orbitals (HOFOs), which we use to identify the highest occupied molecular orbital (HOMO). The anion gave rise to the HOMO for 25 of the 37 ILs studied here. For 10 of the ILs, the energies of the cationic and anionic HOFOs were the same (within experimental error); therefore, it could not be determined whether the HOMO was from the cation or the anion. For two of the ILs, the HOMO was from the cation and not from the anion; consequently it is energetically more favourable to remove an electron from the cation than the anion for these two ILs. In addition, we used a combination of area normalisation and subtraction of XP spectra to produce what are effectively XP spectra for individual ions; this was achieved for 10 cations and 14 anions.

Normal and resonant Auger spectroscopy of isocyanic acid, HNCO.

In this paper, we investigate HNCO by resonant and nonresonant Auger electron spectroscopy at the K-edges of carbon, nitrogen, and oxygen, employing soft X-ray synchrotron radiation. In comparison with the isosteric but linear CO2 molecule, spectra of the bent HNCO molecule are similar but more complex due to its reduced symmetry, wherein the degeneracy of the π-orbitals is lifted. Resonant Auger electron spectra are presented at different photon energies over the first core-excited 1s → 10a' resonance. All Auger electron spectra are assigned based on ab initio configuration interaction computations combined with the one-center approximation for Auger intensities and moment theory to consider vibrational motion. The calculated spectra were scaled by a newly introduced energy scaling factor, and generally, good agreement is found between experiment and theory for normal as well as resonant Auger electron spectra. A comparison of resonant Auger spectra with nonresonant Auger structures shows a slight broadening as well as a shift of the former spectra between -8 and -9 eV due to the spectating electron. Since HNCO is a small molecule and contains the four most abundant atoms of organic molecules, the reported Auger electron decay spectra will provide a benchmark for further theoretical approaches in the computation of core electron spectra.

Pyridine as a Resonantly Addressable Group to Study Electron-Transfer Dynamics in Self-Assembled Monolayers

Resonant Auger electron spectroscopy (RAES) in combination with the core-hole clock (CHC) approach represents a unique tool to study femtosecond electron transfer (ET) dynamics in molecular systems and self-assembled monolayers (SAMs) in particular. A most promising experimental strategy to apply this approach to SAMs involves the decoration of the target films with a group, which can be resonantly excited by narrow-band X-rays. Using a series of well-defined SAMs with a terminal pyridine moiety, we demonstrate here that pyridine can be used as such a group, as an alternative to the nitrile group, which has been utilized for this purpose in the past. For these SAMs, we evaluate the characteristic time for ET from the terminal nitrogen atom of the pyridine group through the molecular framework to the substrate and discuss the results in terms of conjugation and coupling of the relevant electronic states in the molecules. The obtained ET times correlate well with the literature values obtained for the analo...

Dynamics of Electron Transfer in Azulene-Based Self-Assembled Monolayers

Azulene is an attractive building block for molecular electronics design owing to the intrinsic charge separation within its sp2-carbon scaffold. In this context, the structure and molecular organization in self-assembled monolayers (SAMs) of unsubstituted and nitrile-functionalized azulenethiolates on Au(111) substrates were studied by a variety of complementary spectroscopic techniques. The molecule of 2-mercapto-6-cyanoazulene was specifically designed to be addressable within the core hole clock approach in the general framework of resonant Auger electron spectroscopy. The azulenic SAMs described herein were documented to be well-defined and densely packed, with their individual molecular constituents oriented upright with respect to the Au surface, but with considerable tilt and twist. The electron transfer (ET) properties of these azulenic SAMs were found to be comparable to those of analogous naphthalene-based monolayers, which suggests that the charge separation and the related dipole moment have ...

Electronic properties of the boroxine-gold interface: evidence of ultra-fast charge delocalization.

We performed a combined experimental and theoretical study of the assembly of phenylboronic acid on the Au(111) surface, which is found to lead to the formation of triphenylboroxines by spontaneous condensation of trimers of molecules. The interface between the boroxine group and the gold surface has been characterized in terms of its electronic properties, revealing the existence of an ultra-fast charge delocalization channel in the proximity of the oxygen atoms of the heterocyclic group. More specifically, the DFT calculations show the presence of an unoccupied electronic state localized on both the oxygen atoms of the adsorbed triphenylboroxine and the gold atoms of the topmost layer. By means of resonant Auger electron spectroscopy, we demonstrate that this interface state represents an ultra-fast charge delocalization channel. Boroxine groups are among the most widely adopted building blocks in the synthesis of covalent organic frameworks on surfaces. Our findings indicate that such systems, typically employed as templates for the growth of organic films, can also act as active interlayers that provide an efficient electronic transport channel bridging the inorganic substrate and organic overlayer.

Probing charge transfer dynamics in self-assembled monolayers by core hole clock approach

This article reviews recent progress in the application of core hole clock approach in the framework of resonant Auger electron spectroscopy to the monomolecular assembles of alkyl, oligophenyl, and oligo(phenylene–ethynylene) based molecules on Au(111) substrates, referring mostly to the work by the author et al. The major goal was to study electron transfer (ET) dynamics in these systems serving as prototypes of molecular electronics (ME) devices. The ET pathway to the conductive substrate was unambiguously defined by resonant excitation of the nitrile tailgroup attached to the molecular backbone. Characteristic ET times within the femtosecond domain were determined, along with the attenuation factors for the ET dynamics, analogous to the case of the static transport. The above parameters were found to exhibit strong dependence on the character of the molecular orbital which mediates the ET process. In addition, certain spectral features, which can be associated with an inverse ET from the molecular backbone to the excitation site, were observed upon exchange of the nitrile group by strongly electronegative nitro moiety. The reported results represent a valuable input for theory and a certain potential for applications such as ME devices where optimization of ET can have significant technological impact.

Nitro-Substituted Aromatic Thiolate Self-Assembled Monolayers: Structural Properties and Electron Transfer upon Resonant Excitation of the Tail Group

Self-assembled monolayers (SAMs) of HS-(C6H4)n-NO2 (nPT-NO2), abbreviated individually as PT-NO2, BPT-NO2, and TPT-NO2 for n = 1, 2, and 3, respectively, were prepared on Au(111) substrates and characterized by X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and resonant Auger electron spectroscopy. All molecules in the films were found to be bound to the substrate via the thiolate anchor and to have an upright orientation. The introduction of the nitro tail group had a positive effect on the quality of the PT-NO2 SAMs, which was superior to that of the nonsubstituted analogues. The parameters of the BPT-NO2 and TPT-NO2 films were similar to those of the analogous nonsubstituted systems. The [N 1s]π* and [O 1s]π* decay spectra of all studied nPT-NO2 SAMs did not exhibit any trace of charge (electron) transfer (CT) through the molecular framework to the substrate, following the resonant excitation of the tail group. This was explained by the energy considerations h...

Static Conductance of Nitrile-Substituted Oligophenylene and Oligo(phenylene ethynylene) Self-Assembled Monolayers Studied by the Mercury-Drop Method

Static charge transport (CT) properties of nitrile-substituted oligophenylenes and oligo(phenylene ethynylene)s (NC-OPh and NC-OPE, respectively) assembled via the thiolate anchor on gold substrates were measured by the mercury drop junction technique. The derived attenuation factors (β), viz. 0.53 ± 0.1 and 0.30 ± 0.08 Å–1 for the NC-OPh and NC-OPE monolayers, respectively, correlate well with the literature values for the analogous nonsubstituted systems, suggesting that the attachment of the nitrile group to the OPh or OPE backbone does not significantly affect their transport properties. This finding provides a basis for the use of the nitrile moiety as a resonantly addressable group and as specific charge injection site in the measurements of dynamic CT by resonant Auger electron spectroscopy. The comparison between the static and dynamic β values for the NC-OPh monolayers implies that the static value corresponds to nonresonant injection conditions. This suggests, potentially, that the static CT can be performed more efficiently by controlling the specific molecular orbitals into which charge carriers are injected.

On the absence of resonance in the valence band photoemission at L2 resonance edge and the delayed onset of the normal Auger-decay

No clear resonance is present in the resonant valence band photoemission spectrum of a Mn6 (S=4) single molecule magnet grafted on Au (111) for photon energy at the L2 resonance edge. This is due to the L2-hole’s dominant decay by the L2–L3V Coster–Kronig (CK) decay. The excess energy of the photon at which the Mn resonant Raman scattering regime transits to the normal Mn Auger-decay regime in MnO depends on the Mn Auger-decay channels. This is because of the localization and delocalization of two holes in the Auger final states. The Mn resonant Auger-electron spectroscopy spectra of MnO are analyzed.

Inner-shell spectroscopy and exchange interaction of Rydberg electrons bound by singly and doubly charged Kr and Xe atoms in small clusters

Surface-site resolved Kr 3d 5/2 − 15p and 3d 5/2 − 16p and Xe 4d 5/2 − 16p and 4d 5/2 − 17p Rydberg excited states in small van der Waals Kr and Xe clusters with a mean size of 〈 N〉 = 15 are investigated by X-ray absorption spectroscopy. Furthermore, surface-site resolved Kr 4s − 25p, 4s − 26p, and 4s − 14p − 15p shakeup-like Rydberg states in small Kr clusters are investigated by resonant Auger electron spectroscopy. The exchange interaction of the Rydberg electron with the surrounding atoms and the induced polarization of the surrounding atoms in the singly and doubly ionized atoms are deduced from the experimental spectra to analyze different surface-site contributions in small clusters, assuming that the corner, edge, face, and bulk sites have 3, 5–6, 8, and 12 nearest neighbor atoms. These energies are almost proportional to the number of the nearest neighbor atoms. The present analysis indicates that small Kr and Xe clusters with 〈 N〉 = 15 have an average or mixture structure between the fcc-like cubic and icosahedron-like spherical structures.

Charge Transfer Time in Alkanethiolate Self-Assembled Monolayers via Resonant Auger Electron Spectroscopy

The dynamics of the charge transfer (CT) in alkanethiolate self-assembled monolayers is addressed by resonant Auger spectroscopy using the core hole clock method. The CT pathway was unambiguously defined by resonant excitation of the nitrile tailgroup attached to the alkyl backbone. The length of this backbone was varied to monitor the respective dependence of the CT time. It was found that, similar to the static conductance, this dependence can be coarsely described by an exponential function with an attenuation factor of 0.93 per methylene unit (0.72 Å−1; a tunneling along the chain was assumed). As a result, the CT time is quite long even for a relatively short alkyl chain; in particular, it is ca. 100 fs for the chain consisting of only four CH2 units. In contrast, the CT time associated with the thiolate headgroup anchor was found to be quite short, viz. 2.3 fs, which suggests an efficient interfacial electronic coupling between the aliphatic backbone of the CnCN molecules and the substrate over the thiolate−gold linkage.

Biphenylnitrile-Based Self-Assembled Monolayers on Au(111): Spectroscopic Characterization and Resonant Excitation of the Nitrile Tail Group

A series of biphenylnitrile-based self-assembled monolayers (SAMs) on Au(111) was characterized by several complementary spectroscopic techniques, including resonant Auger electron spectroscopy (RAES). In spite of the disturbing role of nitrile, the SAMs exhibited high-quality and expected structural behavior, including the odd−even effects, even though with a lower extent than in the analogous nonsubstituted or methyl-substituted systems. A characteristic feature of the target films, and presumably also a general feature of oligophenyl-based SAMs, is a significant twist of the molecular backbone, similar to the situation in the analogous molecular crystals. No perceptible signal related to tail group-to-substrate transfer of the resonantly excited electron was recorded in the RAES spectra of the target films, even though such a transfer is energetically allowed in some of the cases. This was tentatively explained by the hypothesis that the charge transfer time is too long and lies beyond the range accessible by the core hole clock method via RAES in the present case. A characteristic feature of the RAES spectra of the target films at the excitation to the out-of plane orbital of the nitrile group is a strong suppression of the participator lines. This effect was qualitatively explained by the fact that the initial N1s core vacancy, the vacancy in the out-of-plane π1(C≡N*) orbital, and another valence vacancy participating in the decay are not localized on the same site in the case of this particular orbital and participator decay channels.