Inner-shell Photoelectron Spectroscopy Research Articles

Inner-shell photoelectron spectroscopy unveils the interplay between hydrogen bonds and π−π stacking in clusters of biomolecules in the gas phase: hypoxanthine clusters as a case study

We present a joint theoretical-experimental study on the inner-shell photoionization of hypoxanthine clusters in the gas phase. Simulations were performed using a computational strategy that combines molecular dynamics to explore the conformers of the clusters, density functional theory for geometry optimization and inner shell photoionization calculations. Two main intermolecular interactions are observed: hydrogen-bonds (HB) and π−π stacking. When increasing the cluster size, a combination of both kinds of interaction occurs. We show that such intermolecular interactions play a role in the chemical shift observed in X-ray photoemission spectroscopy experiments. In particular, we highlight the interplay between charge depletion and charge accumulation in regions where HBs stabilize the clusters.

A localized view on molecular dissociation via electron-ion partial covariance

Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d3/2 and 4d5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site.

Dissociation and ionization dynamics of CF3I and CH3I molecules via pump-and-probe experiments using soft x-ray free-electron laser

The dissociation and ionization dynamics of CF3I and CH3I molecules were investigated using a pump-and-probe technique that employs a soft x-ray free-electron laser (SACLA) in Japan. First, time-resolved inner-shell photoelectron spectroscopy was employed to observe the ultrafast reaction of CF3I by monitoring iodine 4d electrons. The change in the I 4d state observed in the photoelectron spectra is found to occur with a rise time τ of approximately 40 fs after a pump laser pulse, which is faster than that observed when an ultrafast gas-phase electron diffraction technique is employed. This implies that the inner-shell photoelectron spectroscopy is more sensitive to the potential surface near the Franck–Condon region. Second, a strong laser intensity at 266 nm, corresponding to a power density of 1.9 × 1014 W cm−2, can easily ionize CH3I molecules via multiphoton ionization processes, and the time dependence of the valence photoelectron spectra clearly shows that at the picosecond timescale, this pump laser pulse causes spectral peaks to shift owing to space-charge effects in response to the large amount of ions generated. Thus, the SACLA can be a useful tool to investigate not only the dynamical process of molecular dissociation but also the ionization process through the shift in the peaks of photoelectron spectra.

Femtochemistry under scrutiny: Clocking state-resolved channels in the photodissociation of CH3I in the A-band.

Clocking of electronically and vibrationally state-resolved channels of the fast photodissociation of CH3I in the A-band is re-examined in a combined experimental and theoretical study. Experimentally, a femtosecond pump-probe scheme is employed in the modality of resonant probing by resonance enhanced multiphoton ionization (REMPI) of the methyl fragment in different vibrational states and detection through fragment velocity map ion (VMI) imaging as a function of the time delay. We revisit excitation to the center of the A-band at 268 nm and report new results for excitation to the blue of the band center at 243 nm. Theoretically, two approaches have been employed to shed light into the observations: first, a reduced dimensionality 4D nonadiabatic wavepacket calculation using the potential energy surfaces by Xie et al. [J. Phys. Chem. A 104, 1009 (2000)]; and second, a full dimension 9D trajectory surface-hopping calculation on the same potential energy surfaces, including the quantization of vibrational states of the methyl product. In addition, high level ab initio electronic structure calculations have been carried out to describe the CH3 3pz Rydberg state involved in the (2 + 1) REMPI probing process, as a function of the carbon-iodine (C-I) distance. A general qualitative agreement is obtained between experiment and theory, but the effect of methyl vibrational excitation in the umbrella mode on the clocking times is not well reproduced. The theoretical results reveal that no significant effect on the state-resolved appearance times is exerted by the nonadiabatic crossing through the conical intersection present in the first absorption band. The vibrationally state resolved clocking times observed experimentally can be rationalized when the (2 + 1) REMPI probing process is considered. None of the other probing methods applied thus far, i.e., multiphoton ionization photoelectron spectroscopy, soft X-ray inner-shell photoelectron spectroscopy, VUV single-photon ionization, and XUV core-to-valence transient absorption spectroscopy, have been able to provide quantum state-resolved (vibrational) clocking times. More experiments would be needed to disentangle the fine details in the clocking times and dissociation dynamics arising from the detection of specific quantum-states of the molecular fragments.

Detecting coherent core-hole wave-packet dynamics in N2 by time- and angle-resolved inner-shell photoelectron spectroscopy

We propose an imaging technique to follow core-hole wave-packet oscillations in the nitrogen molecule. In this scheme, an attosecond x-ray pulse core-ionizes the nitrogen molecule and a subsequent attosecond x-ray pulse probes the evolution of the electron dynamics. We can image the oscillation of the core-hole between the two atomic sites by measuring the angular correlation between photoelectrons. Analytical relations for the angular correlation are derived based on the plane-wave approximation for the photoelectron wave function. We validate these results with a scattering calculation for the photoelectron wave function. The feasibility of the experimental realization of this scheme is discussed in light of current and future capabilities of x-ray free-electron lasers.

Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom

Due to its element- and site-specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH$_3$I) is investigated by ionization above the iodine 4d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.

Changing role of carrier gas in formation of ethanol clusters by adiabatic expansion.

Adiabatic expansion of molecular vapors is a celebrated method for producing pure and mixed clusters of relevance in both applied and fundamental studies. The present understanding of the relationship between experimental conditions and the structure of the clusters formed is incomplete. We explore the role of the backing/carrier gas during adiabatic expansion of ethanol vapors with regard to cluster production and composition. Single-component clusters of ethanol were produced over a wide size-range by varying the rare gas (He, Ar) backing pressure, with Ar being more efficient than He in promoting the formation of pure ethanol clusters. However, at stagnation pressures Ps>1.34(4) bar and temperature 49(2) °C, synchrotron-based valence and inner-shell photoelectron spectroscopy reveals condensation of Ar carrier gas on the clusters. Theoretical calculations of cluster geometries as well as chemical shifts in carbon 1s ionization energies confirm that the experimental observations are consistent with an ethanol core covered by an outer shell of argon. Experiments on the 1-propanol/Ar system display a similar pattern as described for ethanol/Ar, indicating a broader range of validity of the results.

EUV and soft X-ray photoelectron spectroscopy of isolated atoms and molecules using single-order laser high-harmonics at 42 eV and 91 eV

Photoelectron spectroscopy of isolated atoms and molecules using single-order high-harmonics of Ti:Sapphire laser pulses (800 nm, 12 fs/30 fs) is demonstrated. Dielectric multilayer mirrors, SiC/Mg and Mo/Si, are used to isolate the 27th (42 eV) and 59th (91 eV) order harmonics, respectively. The obtained harmonics are characterized by valence and inner-shell photoelectron spectroscopy of Xe. The applications to two-color two-photon ionization of He and pump-probe spectroscopy of ultrafast photodissociation of Br 2, Br 2(C 1Π u) → Br( 2P 3/2) + Br( 2P 3/2), are presented.

Photoinduced Reconfiguration Cycle in a Molecular Adsorbate Layer Studied by Femtosecond Inner-Shell Photoelectron Spectroscopy

A time-resolved study of core-level chemical shifts in a monolayer of aromatic molecules reveals complex photoinduced reaction dynamics. The combination of electron spectroscopy for chemical analysis and ultrashort pulse excitation in the extreme ultraviolet allows performing time-correlated 4d-core-level spectroscopy of iodine atoms that probe the local chemical environment in the adsorbate molecule. The selectivity of the method unveils metastable molecular configurations that appear about 50 ps after the excitation and are efficiently quenched back to the ground state.

Inner-shell photoelectron spectroscopy of size-selected Cu-clusters on Si

Size-selected Cu n + clusters have been deposited onto a p-doped Si-wafer and have been spectroscopically studied by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES). At a cluster coverage of >10 14 cm −2 the XANES and XPS spectra appear very similar to the bulk while X-ray spectra of individual, non-agglomerated clusters are observed at a cluster coverage of <8 × 10 12 cm −2. In the latter spectra, both the L-absorption edge as well as the 2p core ionization potential are higher in energy than the respective bulk value. For all measured clusters the L 3-edge is located above the corresponding 2p 3/2 ionization energy similar to the bulk. Additionally, the absorption energy of the L-edge decreases with increasing cluster size. Upon oxidation of the cluster a strong excitonic absorption feature appears below the core ionization potential (2p 3/2).

Applicability of monochromatized high harmonic extended ultraviolet radiation for inner-shell photoelectron spectroscopy

A laboratory light source for extended ultraviolet (EUV) radiation was realized utilizing high harmonic radiation from intense femtosecond laser light. Utilizing a multilayer monochromator three harmonic orders with photon energies ranging from 66.7 to 72.9 eV can individually be selected to perform inner-shell photoelectron spectroscopy on gas phase as well as surface targets. Examples of spectroscopic studies on free xenon atoms, clean W and GaAs surfaces and I 2 or W(CO) 6 adsorbates emphasize different properties of this new light source like photon flux, spectral resolution and purity, polarization and sensitivity.