Photoelectron Imaging Spectroscopy Research Articles

Reactivity of Polynuclear Niobium Oxynitride Cluster Anions Nb4N5-xOx- (x = 0-5) toward N2.

The activation of N₂ under mild conditions remains a significant challenge in chemistry. Understanding how the composition of ligands modulates the reactivity of metal centers is pivotal for the rational design of efficient catalysts for nitrogen fixation. Herein, the reactions between polynuclear niobium oxynitride anions Nb4N5-xOx- (x = 0-5) and N2 were investigated by employing mass spectrometry, photoelectron imaging spectroscopy, and theoretical calculations. The rate constants of Nb4N5-xOx-/N2 gradually decrease for x = 0 to x = 4, and then increase again for x = 5. The sharp increase of the rate constants of Nb4O5-/N2 corresponds to a decrease in the electron detachment energy of the Nb4O5- cluster in the photoelectron spectroscopic experiment. Theoretical calculations suggest that the low-coordinated Nb-Nb site in Nb4N5-xOx- (x = 0-5) behaves as the active center to bind N2 in the side-on/end-on manner. Mechanistic analysis reveals that raising the O/N ratio leads to higher electron densities on the active Nb-Nb center and decreased positive charge on the metal atoms, which hinders the approach of N2 to the clusters. This finding discloses fundamental insights into the impact of N/O ratios in fine-tuning the reactivity of metal centers towards N2 adsorption in related catalytic processes.

XUV-beamline for photoelectron imaging spectroscopy with shaped pulses.

We introduce an extreme ultraviolet (XUV)-beamline designed for the time-resolved investigation and coherent control of attosecond (as) electron dynamics in atoms and molecules by polarization-shaped as-laser pulses. Shaped as-pulses are generated through high-harmonic generation (HHG) of tailored white-light supercontinua (WLS) in noble gases. The interaction of shaped as-pulses with the sample is studied using velocity map imaging (VMI) techniques to achieve the differential detection of photoelectron wave packets. The instrument consists of the WLS-beamline, which includes a hollow-core fiber compressor and a home-built 4f polarization pulse shaper, and the high-vacuum XUV-beamline, which combines an HHG-stage and a versatile multi-experiment vacuum chamber equipped with a home-built VMI spectrometer. The VMI spectrometer allows the detection of photoelectron wave packets from both the multiphoton ionization (MPI) of atomic or molecular samples by the tailored WLS-pulses and the single-photon ionization (SPI) by the shaped XUV-pulses. To characterize the VMI spectrometer, we studied the MPI of xenon atoms by linearly polarized WLS pulses. To validate the interplay of these components, we conducted experiments on the SPI of xenon atoms with linearly polarized XUV-pulses. Our results include the reconstruction of the 3D photoelectron momentum distribution (PMD) and initial findings on the coherent control of the PMD by tuning the spectrum of the XUV-pulses with the spectral phase of the WLS. Our results demonstrate the performance of the entire instrument for HHG-based photoelectron imaging spectroscopy with prototypical shaped pulses. Perspectively, we will employ polarization-tailored WLS-pulses to generate polarization-shaped as-pulses.

Glory interference spectroscopy in Sr atom

Slow (meV) photoelectron imaging spectroscopy is employed in the experimental study of near-threshold photoionization of strontium atoms in the presence of an external static electric field. Specifically, the study is devoted to the glory effect, that is, the appearance of an intense peak at the center of the recorded photoelectron images, when dealing with m= 0 final ionized Stark states (m denoting the magnetic quantum number). This critical effect is formally identical to that encountered in classical scattering theory, where, for a nonzero value of the impact parameter, the zero-crossing of the deflection function leads to a divergent classical differential cross section. By recording the magnitude variation of this glory peak as a function of electron excitation energy, we observe that, besides the traces of classical origin, it also exhibits intense quantum interference and beating phenomena, above and below the zero-static-field ionization threshold. We study both, single- and two-photon ionization of Sr, thus enabling a comparison not only between the different excitation schemes, but also with an earlier work devoted to two-photon ionization of Mg atom by Kalaitzis et al (2020 Phys. Rev. A 102 033101). Our recordings are analyzed within the framework of the Harmin–Fano frame transformation Stark effect theory that is applied to both the hydrogen atom and a non-hydrogenic one simulating Sr. We discuss the various aspects of the recorded and calculated glory interference and beating structures and their ‘short time Fourier transforms’ and classify them as either atom-specific or atom independent. In particular, we verify the ‘universal’ connection between the glory oscillations above the zero-field threshold and the differences between the origin-to-detector times of flight corresponding to pairs of classical electron trajectories that end up to the image center.

Observation of bound valence excited electronic states of deprotonated 2-hydroxytriphenylene using photoelectron, photodetachment, and resonant two-photon detachment spectroscopy of cryogenically cooled anions.

Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants, and they are also ubiquitous in the interstellar medium. Here, we report the study of a complex O-containing PAH anion, the deprotonated 2-hydroxytriphenylene (2-OtPh-), using high-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled anions. Vibrationally resolved photoelectron spectra yield the electron affinity of the 2-OtPh radical as 2.629(1) eV and several vibrational frequencies for its ground electronic state. Photodetachment spectroscopy reveals bound valence excited electronic states for the 2-OtPh- anion, with unprecedentedly rich vibronic features. Evidence is presented for a low-lying triplet state (T1) and two singlet states (S1 and S2) below the detachment threshold. Single-color resonant two-photon photoelectron spectroscopy uncovers rich photophysics for the 2-OtPh- anion, including vibrational relaxation in S1, internal conversion to the ground state of 2-OtPh-, intersystem crossing from S2 to T1, and a long-lived autodetaching shape resonance about 1.3eV above the detachment threshold. The rich electronic structure and photophysics afforded by the current study suggest that 2-OtPh- would be an interesting system for pump-probe experiments to unravel the dynamics of the excited states of this complex PAH anion.

Photoelectron Imaging Signature for Selective Formation of Icosahedral Anionic Silver Cages Encapsulating Group 5 Elements: M@Ag12- (M = V, Nb, and Ta).

An assembly of 13 atoms can form highly symmetric architectures like those belonging to D3h, Oh, D5h, and Ih point groups. Here, using photoelectron imaging spectroscopy in combination with density functional theory (DFT) calculations, we present a simple yet convincing experimental signature for the selective formation of icosahedral cages of anionic silver clusters encapsulating a dopant atom of group 5 elements: M@Ag12- (M = V, Nb, and Ta). Their photoelectron images obtained at 4 eV closely resemble one another: only a single ring is observed, which is assignable to photodetachment signals from a 5-fold degenerate superatomic 1D electronic shell in the 1S21P61D10 configuration of valence electrons. The perfect degeneracy represents an unambiguous fingerprint of an icosahedral symmetry, which would otherwise be lifted in all of the other structural isomers. DFT calculations confirm that Ih forms are the most stable and that D5h, Oh, and D3h structures are not found even in metastable states.

Channel Competition and Control of Relaxation Pathways in S1 State of Acrolein: Role of Conical Intersection and Surface Crossing.

Channel competition and further photochemical control of relaxation pathways in excited molecules are of primary importance in photochemistry and related areas. Acrolein, as the simplest and most typical α,β-enone, is suitable to provide a model for understanding the photochemistry and photophysics of α,β-enones. Here, the ultrafast dynamics in acrolein following S1(nπ*) excitation has been studied by time-resolved photoelectron imaging (TRPEI) and mass spectroscopy. The competition between intersystem crossing (ISC) and internal conversion (IC) is investigated. The key factor influencing the decay pathways and the relative contributions are revealed to be the position of the excitation relative to the energy of the S1/S0 conical intersection (CI), which is obtained to be 3.65-3.76 eV experimentally. If the excitation is above the CI, IC is superior to ISC and most excited molecules go back to the ground. Otherwise, ISC will dominate the relaxation and lead the triplet products formation. These results show the potential of affecting the dynamics and governing the fate of excited molecules by adjusting the excitation conditions from the point of view of chemical control.

Rydberg state dynamics and fragmentation mechanism of N,N,N',N'-tetramethylmethylenediamine.

The non-adiabatic relaxation processes and the fragmentation dynamics of Rydberg-excited N,N,N',N'-tetramethylmethylenediamine (TMMDA) are investigated using femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy. Excitation at 208nm populates TMMDA in a charge-localized 3p state. Rapid internal conversion (IC) to 3s produces two charge-delocalized conformers with independent time constants and distinct population ratios. As the system explores the 3s potential surface, the structural evolution continues on a 1.55ps timescale, followed by a slower (12.1ps) relaxation to the ground state. A thorough comparison of the time-dependent mass and photoelectron spectra suggests that ionization out of the 3p state ends up with the parent ion, the vibrational energy of which is insufficient for the bond cleavage. On the contrary, by virtue of the additional energy acquired by IC from 3p, the internal energy deposited in 3s is available to break the C-N bond, leading to the fragment ion. The fragmentation is found to occur on the ion surface instead of the Rydberg surface.

Dissociative photoionization studies of ethyl iodide using synchrotron radiation photoionization mass spectrometry and photoelectron imaging

The stepwise dissociative photoionization of ethyl iodide(C2H5I) has been investigated via synchrotron radiation photoionization mass spectrometry and photoelectron imaging spectroscopy. By using VUV synchrotron radiation as excitation source, the photoionization and stepwise dissociative photoionization of C2H5I were observed by tuning the photon energy from 8.5 to 14.0 eV. The ionization energy of C2H5I was measured to be 9.33 ± 0.05 eV, and the appearance energies of C2H5+, C2H4+, C2H3+ were also determined according to the photoionization efficiency spectra. The possible pathways of the stepwise dissociation of C2H5I were determined by combining the experiments with theoretical calculation based on DFT. Finally, the multi-photon ionization process of C2H5I molecule was further studied via intensity-dependent photoelectron imaging spectroscopy.

Investigation of the Electronic and Vibrational Structures of the 2-Furanyloxy Radical Using Photoelectron Imaging and Photodetachment Spectroscopy via the Dipole-Bound State of the 2-Furanyloxide Anion.

The 2-furanyloxy radical is an important chemical reaction intermediate in the combustion of biofuels and aromatic compounds. We report an investigation of its electronic and vibrational structures using photoelectron and photodetachment spectroscopy and resonant photoelectron imaging (PEI) of cryogenically cooled 2-furanyloxide anion. The electron affinity of 2-furanyloxy is measured to be 1.7573(8) eV. Two excited electronic states are observed at excitation energies of 2.14 and 2.82 eV above the ground state. Photodetachment spectroscopy reveals a dipole-bound state 0.0143 eV below the detachment threshold and 25 vibrational Feshbach resonances for the 2-furanyloxide anion. The combination of photodetachment spectroscopy and resonant PEI yields frequencies for 18 out of a total of 21 vibrational modes for the 2-furanyloxy radical, including all six of its bending modes. The rich electronic and vibrational information will be valuable for further understanding the role of 2-furanyloxy as a key reaction intermediate of combustion and atmospheric interests.

Catalytic NO Reduction by NO Pre-Adsorbed RhCeO2 NO- Clusters.

A fundamental understanding on the dynamically structural evolution of catalysts induced by reactant gases under working conditions is challenging but pivotal in catalyst design. Herein, in combination with state-of-the-art mass spectrometry for cluster reactions, cryogenic photoelectron imaging spectroscopy, and quantum-chemical calculations, we identified that NO adsorption on rhodium-cerium bimetallic oxide cluster RhCeO2 - can create a Ce3+ ion in product RhCeO2 NO- that serves as the starting point to trigger the catalysis of NO reduction by CO. Theoretical calculations substantiated that the reduction of another two NO molecules into N2 O takes place exclusively on the Ce3+ ion while Rh behaves like a promoter to buffer electrons and cooperates with Ce3+ to drive NO reduction. Our finding demonstrates the importance of NO in regulating the catalytic behavior of Rh under reaction conditions and provides much-needed insights into the essence of NO reduction over Rh/CeO2 , one of the most efficient components in three-way catalysts for NOx removal.

Probing the geometric and electronic structures of the lanthanide oxide HoOn–1/0 (n = 1–3) clusters

The complex 4f and 5d orbits of lanthanide oxide clusters increases the complexity and difficulty in both theoretical and experimental research. Combining the photoelectron imaging spectroscopy and ab initio calculations, the structural and electronic properties of HoO– were studied. The adiabatic detachment energy (ADE) and vertical detachment energy (VDE) of HoO– have been measured to be 1.31(3) eV and 1.42(2) eV, respectively. To determine the vibrational structure and observed spectral bands in the photoelectron spectrum, Franck-Condon simulation of the ground-state transition for HoO– has been performed. The fundamental frequency of ground-state HoO is estimated to be 893 ± 73 cm−1. Density functional method (DFT) was used to study the neutral and anionic clusters of HoOn–1/0 (n = 1–3), and the most stable cluster structures were obtained. Based on the DFT calculations, the theoretical ADEs and VDEs of anionic HoOn– (n = 1–3) clusters were obtained and the photoelectron spectra (PES) of HoOn– (n = 1–3) clusters were simulated, which might stimulate further experimental investigations on the Ho oxide clusters. In addition, the corresponding molecular orbitals (MOs) were also discussed to reveal the interaction between Ho and O atoms. This study can help us to understand the chemical bonding in Ho-containing molecules and will provide some light in their surface chemistry and photochemistry investigation.

Dinitrogen Activation and Functionalization by Heteronuclear Metal Cluster Anions FeV2C2- at Room Temperature.

It is of great importance to study the mechanisms to activate dinitrogen (N2), the very inert molecule, under mild conditions. Gas-phase metal clusters are being actively generated to react with N2 to identify new reaction types and mechanisms. Herein, an unprecedented, mechanistically unique metal atom (Fe or V) ejection in the thermal reaction of FeV2C2- with N2 has been identified using mass spectrometry, photoelectron imaging spectroscopy, and quantum chemistry calculations. Strong evidence suggests that the complete cleavage of the N≡N triple bond and subsequent functionalization of two N atoms via C-N coupling were achieved in this reaction. The complementary cooperation between V atoms with strong electron-donating ability and an Fe atom with large electron-withdrawing ability as well as the geometric flexibility of the Fe-V-V ring drives the whole reaction. The important role of C ligands in N≡N cleavage was also revealed. This study emphasizes the importance of heteronuclear metal systems for N2 fixation.

Chirality detection of surface desorption products using photoelectron circular dichroism.

Chirality detection of gas-phase molecules at low concentrations is challenging as the molecular number density is usually too low to perform conventional circular dichroism absorption experiments. In recent years, new spectroscopic methods have been developed to detect chirality in the gas phase. In particular, the angular distribution of photoelectrons after multiphoton laser ionization of chiral molecules using circularly polarized light is highly sensitive to the enantiomeric form of the ionized molecule [multiphoton photoelectron circular dichroism (MP-PECD)]. In this paper, we employ the MP-PECD as an analytic tool for chirality detection of the bicyclic monoterpene fenchone desorbing from a Ag(111) crystal. We record velocity-resolved kinetics of fenchone desorption on Ag(111) using pulsed molecular beams with ion imaging techniques. In addition, we measure temperature-programmed desorption spectra of the same system. Both experiments indicate weak physisorption of fenchone on Ag(111). We combine both experimental techniques with enantiomer-specific detection by recording MP-PECD of desorbing molecules using photoelectron imaging spectroscopy. We can clearly assign the enantiomeric form of the desorption product fenchone in sub-monolayer concentration. The experiment demonstrates the combination of MP-PECD with surface science experiments, paving the way for enantiomer-specific detection of surface reaction products on heterogeneous catalysts for asymmetric synthesis.

High-Resolution Photoelectron Imaging and Photodetachment Spectroscopy of Cryogenically Cooled IO–

We report a high-resolution photoelectron imaging and photodetachment spectroscopy study of cryogenically-cooled IO-. The high-resolution photoelectron spectra yield a more accurate electron affinity (EA) of 2.3805(5) eV for IO, as well as a more accurate spin-orbit splitting energy between 2Π3/2 and 2Π1/2 of IO as 2093(5) cm-1. Photodetachment spectroscopy revealed for the first time several excited states for the IO- anion, including two valence-type excited states, the repulsive 3Π state and a shallow bound 1Π state. More interestingly, we have observed two vibrational resonances which are proposed to be due to a dipole-induced resonant state, about 230 cm-1 above the detachment threshold of IO-.

A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V3C4.

Cleavage of the triple N≡N bond by metal clusters is of fundamental interest and practical importance in nitrogen fixation. Previous studies of N≡N bond cleavage by gas-phase metal clusters emphasized the importance of the dinuclear metal centers. Herein, the dissociative adsorption of N2 and subsequent C-N coupling on trinuclear carbide cluster anions V3C4- under thermal collision conditions have been characterized by employing mass spectrometry (collision induced dissociation), cryogenic photoelectron imaging spectroscopy, and quantum chemistry calculations. A theoretical analysis identified a crucial adsorption intermediate with N2 bonded with the V3 metal core in the end-on/side-on/side-on (ESS) mode, which most likely enables the facile cleavage of the N≡N bond. Such a vital N2 coordination in the ESS mode is a result of symmetry-matched interactions between the occupied orbitals of the metal core and both of the two empty π* orbitals of N2. Furthermore, carbon ligands also play a considerable role in enhancing the reactivity of the metal core toward N2. This study strongly suggests a new mechanism of N≡N bond cleavage by gas-phase metal clusters.

Side-on-End-on Coordination of Dinitrogen on a Polynuclear Vanadium Nitride Cluster Anion [V5 N5

The side-on-end-on coordination of N2 can be very important to activate and functionalize this very stable molecule. However, such coordination has rarely been reported. This study reports a gas-phase species (a polynuclear vanadium nitride cluster anion [V5 N5 ]- ) that can capture N2 efficiently (12 %), and the quantum chemistry modelling suggests an unusual side-on-end-on coordination. The cluster anions were generated by laser ablation and the reaction with N2 has been characterized by mass spectrometry, photoelectron imaging spectroscopy, and density functional theory calculations. The back-donation interactions between the localized d-d bonding orbitals on the low-coordinated dual metal (V) sites and the antibonding π* orbitals of N2 are the driving forces to adsorb N2 with a high binding energy (about 2.0 eV).

Unraveling electronic states and relaxation dynamics in ultraviolet excited crotonaldehyde via femtosecond time-resolved photoelectron imaging

Real-time evolution of S1 state crotonaldehyde is tracked by utilizing femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy with UV excitation. Our experimental results show that crotonaldehyde molecule has experienced a quick internal conversion to the ground state in an ultrafast timescale of <100 fs following excitation to S1 state both with 310 nm and 365 nm pumping. In addition, the energy of 3s and different 3p Rydberg states of crotonaldehyde were assigned to be 3s = 6.98 ± 0.11 eV, 3py = 7.30 ± 0.08 eV, 3px = 7.63 ± 0.04 eV, and 3pz = 7.79 ± 0.03 eV by combining the multi-peak time-resolved photoelectron spectroscopy and quantum chemistry calculation results.

Sensitive Detection of Gas-Phase Glyoxal by Electron Attachment Reaction Ionization Mass Spectrometry.

Glyoxal (GLY) acts as a key contributor to tropospheric ozone production and secondary organic aerosol (SOA) formation on local to regional scales. The detection of GLY provides useful indicators of fast photochemistry occurring in the lower troposphere. The fast and sensitive detection of GLY is thus important, while traditional chemical ionization such as the proton-transfer reaction (PTR) is extremely limited by the poor detection limit and extensive fragmentation. To address these limitations, electron attachment reaction (EAR) ionization was applied to detect GLY. The generation of parent anions (GLY-) without fragmentation was observed, and cryogenic photoelectron imaging spectroscopy further characterized the structure of GLY-. The detection limit was estimated to be as low as (52 ± 1) pptv (parts per trillion by volume) with 1 min measurements. Other components in ambient air, such as water, carbon dioxide, and trace gases (acetone, propanal, etc.) have no effect on the detection of GLY. The EAR ionization is more promising than PTR ionization in detecting GLY. The detection of GLY in ambient air by the EAR ionization has been demonstrated.

Time-Resolved Photoelectron Imaging of Acetone with 9.3 eV Photoexcitation

Ultrafast electronic relaxation following 9.3 eV photoexcitation of gaseous acetone was investigated with time-resolved photoelectron imaging spectroscopy. An intense photoionization signal due to a transition from the 41A1(π,π*) state to the D1(π-1) cationic state diminishes within 50 fs, owing to vibrational wave packet motion leaving our observation energy window. Additional photoionization signals were assigned to transitions from Rydberg states with principal quantum numbers of 3-8 to the D0(n-1) cationic state, created by strong vibronic couplings with the bright 41A1(π,π*) state. The deactivation processes of the 41A1(π,π*) and Rydberg states are discussed based on their decay profiles obtained from a time-energy map of photoelectron kinetic energy distributions.

Size-Dependent Association of Cobalt Deuteride Cluster Anions Co3Dn- (n = 0-4) with Dinitrogen.

Dinitrogen (N2) activation by metal hydride species is of fundamental interest and practical importance while the role of hydrogen in N2 activation is not well studied. Herein, the structures of Co3Dn- (n = 0-4) clusters and their reactions with N2 have been studied by using a combined experimental and computational approach. The mass spectrometry experiments identified that the Co3Dn- (n = 2-4) clusters could adsorb N2 while the Co3Dn- (n = 0 and 1) clusters were inert. The photoelectron imaging spectroscopy indicated that the electron detachment energies of Co3D2-4- are smaller than those of Co3D0,1-, which characterized that it is easier to transfer electrons from Co3D2-4- than from Co3D0,1- to activate N2. The density functional theory calculations generally supported the experimental observations. Further analysis revealed that the H atoms in the Co3Hn- (n = 2-4) clusters generally result in higher energies of the Co 3d orbitals in comparison with the Co3Hn- (n = 0 and 1) systems. By forming chemical bonds with H atoms, the Co atoms of Co3H2-4- are less negatively charged with respect to the naked Co3- system, which leads to higher N2 binding energies of Co3H2-4N2- than that of Co3N2-.