Photoelectron Imaging Spectroscopy Research Articles

Photoelectron imaging spectroscopy and photodynamics of m-xylene cations

The delayed photofragmentation and photoelectron spectroscopy coupled with DFT calculations were employed for the investigation of the relaxation dynamics of m-xylene cations. The multiphoton ionization induced by the pump pulse was used for the preparation of the m-xylene cations, and the population was characterized by the technique of photoelectron imaging. A time-delayed probe pulse was used to excite the prepared m-xylene cations to energetically higher electronic states, which undergo fragmentation. The relaxation dynamics of the m-xylene cations was tracked by monitoring the depletion of excited parent-ion and the formation of the fragment-ion. Two relaxation time constants are determined by monitoring the depletion of the excited parent-ion and the formation of the fragment-ion with the delay time. The first component of τ1 = 764 (±25) fs is attributed to an intramolecular vibrational redistribution process within the D0 state and the slow one of τ2 > 440 ns is ascribed to the long lifetime of the cations.

High-resolution photoelectron imaging and resonant photoelectron spectroscopy via noncovalently bound excited states of cryogenically cooled anions.

Valence-bound anions with polar neutral cores (μ > ∼2.5 D) can support dipole-bound excited states below the detachment threshold. These dipole-bound states (DBSs) are highly diffuse and the weakly bound electron in the DBS can be readily autodetached via vibronic coupling. Excited DBSs can be observed in photodetachment spectroscopy using a tunable laser. Tuning the detachment laser to above-threshold vibrational resonances yields vibrationally enhanced resonant photoelectron spectra, which are highly non-Franck-Condon with much richer vibrational information. This perspective describes recent advances in the studies of excited DBSs of cryogenically cooled anions using high-resolution photoelectron imaging (PEI) and resonant photoelectron spectroscopy (rPES). The basic features of dipole-bound excited states and highly non-Franck-Condon resonant photoelectron spectra will be discussed. The power of rPES to yield rich vibrational information beyond conventional PES will be highlighted, especially for low-frequency and Franck-Condon-inactive vibrational modes, which are otherwise not accessible from non-resonant conventional PES. Mode-selectivity and intra-molecular rescattering have been observed during the vibrationally induced autodetachment. Conformer-specific rPES is possible due to the different dipole-bound excited states of molecular conformers with polar neutral cores. For molecules with μ ≪ 2.5 D or without dipole moments, but large quadrupole moments, excited quadrupole-bound states can exist, which can also be used to conduct rPES.

Electron Attachment Reaction Ionization of Gas-Phase Methylglyoxal.

Methylglyoxal (MGLY) plays a significant role in atmospheric chemistry by serving as a key contributor to the formation of active free radicals, ozone, and secondary organic aerosol. Detection of MGLY by traditional chemical ionization such as proton-transfer reaction has several shortcomings such as parent molecule fragmentation. In this study, an electron attachment reaction (EAR) ionization method has been developed for the effective detection of MGLY. Almost no fragmentation was observed during the EAR. The generation of MGLY- anion in the EAR was further confirmed by cryogenic photoelectron imaging spectroscopy. The concentration of MGLY can be calibrated by using dibromomethane (CH2Br2) as reference gas. The detection sensitivity of MGLY was estimated to be (100 ± 2) mV/ppbv (parts per billion by volume). The O2, H2O, CO2, and trace gases in ambient air have no obvious effects on the detection of MGLY- anion by the EAR ionization method.

Probing the Geometric and Electronic Structures of the Monogadolinium Oxide GdO n-1/0 ( n = 1-4) Clusters.

The existence of abundant 4f electrons significantly increases the complexity and difficulty in precisely determining the geometric and electronic structures of the lanthanide oxide clusters. Herein, by combining the photoelectron imaging spectroscopy and density functional theory (DFT) calculations, the electronic structure of GdO was investigated. An electron affinity (EA) of 1.16 ± 0.09 eV is obtained, and the measured anisotropy parameter (β) provides direct experimental evidence about the orbital symmetry of the detached electron in GdO-. DFT calculations have been employed to acquire the optimized geometries of the GdO n-1/0 ( n = 2-4) clusters, and multiple activated oxygen species, which are radical, peroxide, superoxide, triradical, and ozonide radical, are found in these oxide clusters. Simulated photoelectron spectra (PES) of the GdO n-1/0 ( n = 2-4) clusters are examined, which may stimulate further experimental investigations on the gadolinium oxide clusters. In addition, the valence molecular orbitals (MOs) of these clusters are also discussed to reveal the interaction between the lanthanide metal (Gd) and O atoms.

Methane Activation by Gas Phase Atomic Clusters.

The increasing supply of natural gas has created a strong demand for developing efficient catalytic processes to upgrade methane, the most stable alkane molecule, into value-added chemicals. Currently, methane conversion in laboratory and industry is mostly performed under high-temperature conditions. A lot of effort has been devoted to exploring chemical entities that are able to activate the C-H bond of methane at lower temperatures, preferably room temperature. Gas phase atomic clusters with limited numbers of atoms are ideal models of active sites on heterogeneous catalysts. The cluster systems are being actively studied to activate methane under room-temperature conditions. State-of-the-art mass spectrometry, photoelectron imaging spectroscopy, and quantum chemistry calculations have been combined in our laboratory to reveal the molecular-level mechanisms of methane activation by atomic clusters. In this Account, we summarize our recent progress on thermal methane activation by metal oxide clusters doped with noble-metal atoms (Au, Pt, and Rh) as well as by oxygen-free species including carbides and borides of base metals (V, Ta, Mo, and Fe). In contrast to the generations of CH3• free radicals in many of the previously reported cluster reactions with methane, the generations of stable products such as formaldehyde, acetylene, and syngas as well as closed-shell species AuCH3 and B3CH3 have been identified for the cluster reaction systems herein. Besides the well recognized mechanisms of methane activation by the O-• radicals through hydrogen atom abstraction and by metal atoms through oxidative addition, the new mechanisms of synergistic methane activation by Lewis acid-base pairs (such as Auδ+-Oδ- and Bδ+-Bδ-) and by dinuclear metal centers (such as Ta-Ta) have been recently revealed. In the reactions between methane and oxide clusters doped with noble-metal atoms, the oxide cluster "supports" can accept the H atoms and the CH x species delivered through the noble-metal atoms and then transform methane into stable oxygenated compounds. The product selectivity (such as formaldehyde versus syngas) can be controlled by different noble-metal atoms (such as Pt versus Rh). The electronic structures of base metal centers can be engineered through carburization so that the low-spin states can be accessible to reduce the C-H bond of methane. Such active base metal centers in low-spin states resemble related noble-metal atoms in methane activation. The boron clusters (such as B3 in VB3+) can be polarized by the metal cations to form the Lewis acid-base pair Bδ+-Bδ- to cleave the C-H bond of methane very easily. These molecular-level mechanisms may well be operative in related heterogeneous catalysis and can be a fundamental basis to design efficient catalysts for activation and conversion of methane under mild conditions.

Quantum dynamics of Rb atoms desorbing off the surface of He nanodroplets

The desorption of excited rubidium (Rb) atoms off the surface of helium (He) nanodroplets is studied in detail using femtosecond time-resolved photoion and photoelectron imaging spectroscopy in combination with quantum wave packet simulations. The good agreement of the measured time-dependent velocity distributions with the simulation when exciting the Rb dopant atoms into the 6p-state supports the pseudo-diatomic model (PDM) for the Rb-He droplet interaction, even on the level of quantum wave packet dynamics. Time-resolved photoelectron spectra reveal the partitioning of excitation energy into the dopant and the droplet degrees of freedom.

Quantum-beat photoelectron-imaging spectroscopy of Xe in the VUV

Time-resolved pump-probe measurements of Xe, pumped at 133~nm and probed at 266~nm, are presented. The pump pulse prepared a long-lived hyperfine wavepacket, in the Xe $5p^5(^2P^{\circ}_{1/2})6s~^2[1/2]^{\circ}_1$ manifold ($E=$77185 cm$^{-1}=$9.57 eV). The wavepacket was monitored via single-photon ionization, and photoelectron images measured. The images provide angle- and time-resolved data which, when obtained over a large time-window (900~ps), constitute a precision quantum beat spectroscopy measurement of the hyperfine state splittings. Additionally, analysis of the full photoelectron image stack provides a quantum beat imaging modality, in which the Fourier components of the photoelectron images correlated with specific beat components can be obtained. This may also permit the extraction of isotope-resolved photoelectron images in the frequency domain, in cases where nuclear spins (hence beat components) can be uniquely assigned to specific isotopes (as herein), and also provides phase information. The information content of both raw, and inverted, image stacks is investigated, suggesting the utility of the Fourier analysis methodology in cases where images cannot be inverted.

Low-Energy Photoelectron Imaging Spectroscopy of Lan(benzene) (n = 1 and 2).

Lan(benzene) (n = 1 and 2) are formed in a pulsed laser-ablation molecular beam source and characterized by low-energy photoelectron imaging spectroscopy. The photoelectron spectrum of La2(benzene) displays a strong origin band, a short metal-ligand stretching progression, and a weak ring deformation band. Four isomers are considered for La2(benzene), and the preferred structure is an inverse sandwich with two La atoms residing on the opposite sides of the benzene ring. The ground electronic state of the inverse sandwich is 1A1g (D3d) with (5dxy,x2-y2 + π*)46s2 electron configuration. Ionization removes a La-based 6s electron and yields a 2A1g ion. The spectrum of La(benzene) is similar to the zero-electron kinetic energy spectrum reported previously by our group, although the spectral line width is somewhat broader. The measurement of the photoelectron angular distribution of La(benzene) confirms that the ejected electron has largely a p wave character. The metal-ligand bonding of La2(benzene) is considerably stronger than that of La(benzene) due to the threefold binding of each La atom in the dilanthanum species and the twofold binding in the monolanthanum complex.

Application of quantitative X‐ray photoelectron spectroscopy (XPS) imaging: investigation of Ni‐Cr‐Mo alloys exposed to crevice corrosion solution

This paper explores quantitative X‐ray photoelectron spectroscopy imaging on three different Ni‐Cr‐Mo Hastelloy® alloys (BC‐1, C‐22 and G‐30) with differing Cr and Mo contents. The alloys were subjected to a simulated critical crevice corrosion solution. Ni‐based alloys have been shown to exhibit excellent resistance to a range of corrosive media due to the formation of an inert oxide layer, primarily containing Cr and Mo. However, these alloys may rapidly corrode in the crevice environment produced by seams, gaskets or deposits of debris on the alloy surface. Understanding how the oxide film is influenced by the Cr and Mo content is crucial in determining an optimal alloy composition that reduces or suppresses the possibility of crevice corrosion. The protective oxide films are very thin in nature, generally several nanometers. XPS imaging was used to monitor changes in oxide film composition and to correlate the distribution of Cr and Mo to the grain structure of the alloys. Copyright © 2017 John Wiley & Sons, Ltd.

Visualization of the formation of cyclopentylcarbene using time-resolved photoelectron imaging spectroscopy

Ultrafast electronic relaxation dynamics in cyclohexene are studied using femtosecond photoelectron imaging spectroscopy. Transient photoelectron kinetic energy distributions and photoelectron angular distributions are obtained and analyzed. Photoelectron bands are discussed and assigned to the ionization of the related electronic states. The formation process of cyclopentylcarbene, together with the ultrafast relaxation of the involved electronic states, is evidenced by the transient photoelectron images. The lifetime for the observed carbene is very short and determined to be 395 (±67) fs. The ionization dynamics of the produced cyclopentylcarbene are also discussed via an analysis of the corresponding photoelectron band.

Real-time visualization of the vibrational wavepacket dynamics in electronically excited pyrimidine via femtosecond time-resolved photoelectron imaging.

The vibrational wavepacket dynamics at the very early stages of the S1-T1 intersystem crossing in photoexcited pyrimidine is visualized in real time by femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy. A coherent superposition of the vibrational states is prepared by the femtosecond pump pulse at 315.3 nm, resulting in a vibrational wavepacket. The composition of the prepared wavepacket is directly identified by a sustained quantum beat superimposed on the parent-ion transient, possessing a frequency in accord with the energy separation between the 6a1 and 6b2 states. The dephasing time of the vibrational wavepacket is determined to be 82 ps. More importantly, the variable Franck-Condon factors between the wavepacket components and the dispersed cation vibrational levels are experimentally illustrated to identify the dark state and follow the energy-flow dynamics on the femtosecond time scale. The time-dependent intensities of the photoelectron peaks originated from the 6a1 vibrational state exhibit a clear quantum beating pattern with similar periodicity but a phase shift of π rad with respect to those from the 6b2 state, offering an unambiguous picture of the restricted intramolecular vibrational energy redistribution dynamics in the 6a1/6b2 Fermi resonance.

Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX- (E = As, P, and N; X = S and O) Anions.

Three newly synthesized [Na+(221-Kryptofix)] salts containing AsCO-, PCO-, and PCS- anions were successfully electrosprayed into a vacuum, and these three ECX- anions were investigated by negative ion photoelectron spectroscopy (NIPES) along with high-resolution photoelectron imaging spectroscopy. For each ECX- anion, a well-resolved NIPE spectrum was obtained, in which every major peak is split into a doublet. The splittings are attributed to spin-orbit coupling (SOC) in the ECX• radicals. Vibrational progressions in the NIPE spectra of ECX- were assigned to the symmetric and the antisymmetric stretching modes in ECX• radicals. The electron affinities (EAs) and SO splittings of ECX• are determined from the NIPE spectra to be AsCO•: EA = 2.414 ± 0.002 eV, SO splitting = 988 cm-1; PCO•: EA = 2.670 ± 0.005 eV, SO splitting = 175 cm-1; PCS•: EA = 2.850 ± 0.005 eV, SO splitting = 300 cm-1. Calculations using the B3LYP, CASPT2, and CCSD(T) methods all predict linear geometries for both the anions and the neutral radicals. The calculated EAs and SO splittings for ECX• are in excellent agreement with the experimentally measured values. The simulated NIPE spectra, which are based on the calculated Franck-Condon factors, and the SO splittings nicely reproduce all of the observed spectral peaks, thus allowing unambiguous spectral assignments. The finding that PCS• has the greatest EA of the three triatomic molecules considered here is counterintuitive based upon simple electronegativity considerations, but this finding is understandable in terms of the movement of electron density from phosphorus in the HOMO of PCO- to sulfur in the HOMO of PCS-. Comparisons of the EAs of PCO• and PCS• with the previously measured EA values for NCO• and NCS• are made and discussed.

Real-time observation of multi-mode vibronic coherence in pentafluoropyridine.

The ultrafast dynamics of pentafluoropyridine in the 1 1B2 (ππ*) electronic state excited at λpump = 255 nm is investigated by femtosecond time-resolved time-of-flight mass spectrometry and photoelectron imaging spectroscopy. A pronounced, long-lived, and complex periodic modulation of the transient ion yield signal with contributions by four distinct frequency components, 72 cm-1, 144 cm-1, 251 cm-1, and 281 cm-1, is observed for up to 9 ps. The recorded photoelectron images display a spectral band from the excited 1 1B2 (ππ*) state only in the oscillation maxima; the signal is strongly reduced in the oscillation minima. Supported by electronic structure calculations at the RI-SCS-CC2 and XMCQDPT2 levels of theory, the oscillating components of the signal are identified as frequencies of b1 symmetry coupling modes in a vibronic coherence of the 1 1B2 (ππ*) and 1 1A2 (πσ*) electronic states. The optical excitation initiates regular and periodic wavepacket motion along those out-of-plane modes. In the distorted molecular structure, the initially excited state acquires substantial πσ* character that modulates the transition dipole moment for ionization and results in the observed oscillations.

Electron affinity and excited states of methylglyoxal.

Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A'), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A') = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A' state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A' ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

Note: Energy calibration of a femtosecond photoelectron imaging detector with correction for the ponderomotive shift of atomic ionization energies.

Femtosecond photoelectron imaging spectroscopy is a powerful technique for following state-resolved molecular transformations in complex coupled potential energy landscapes. To avoid unwanted nonlinear side-effects, the employed laser pulse energies are usually reduced to minimal values. However, the energy calibration of the photoelectron imaging detector is ideally performed using multi-photon above-threshold ionization of suitable atomic species, for which rather high laser intensities are required. In this work, we show that the calibration spectra of xenon obtained with high laser pulse energies cannot be directly used for the evaluation of molecular photoelectron spectra recorded using low-energy laser pulses. The reason is the intensity-dependent AC Stark shift of the atomic ionization energies to larger values, which in turn leads to a corresponding decrease of the photoelectron kinetic energies. We present a simple procedure to quantify this so-called ponderomotive shift and calculate the theoretically expected un-shifted photoelectron energies.

Methane Activation by Tantalum Carbide Cluster Anions Ta2C4.

Methane activation by transition metals is of fundamental interest and practical importance, as this process is extensively involved in the natural gas conversion to fuels and value-added chemicals. While single-metal centers have been well recognized as active sites for methane activation, the active center composed of two or more metal atoms is rarely addressed and the detailed reaction mechanism remains unclear. Here, by using state-of-the-art time-of-flight mass spectrometry, cryogenic anion photoelectron imaging spectroscopy, and quantum-chemical calculations, the cooperation of the two Ta atoms in a dinuclear carbide cluster Ta2C4- for methane activation has been identified. The C-H bond activation takes place predominantly around one Ta atom in the initial stage of the reaction and the second Ta atom accepts the delivered H atom from the C-H bond cleavage. The well-resolved vibrational spectra of the cryogenically cooled anions agree well with theoretical simulations, allowing the clear characterization of the structure of Ta2C4- cluster. The reactivity comparison between Ta2C4- cluster and the carbon-less analogues (Ta2C3- and Ta2C2-) demonstrated that the cooperative effect of the two metal atoms can be well tuned by the carbon ligands in terms of methane activation and transformation.

Electronic structure of the diatomic VO anion: A combined photoelectron-imaging spectroscopic and theoretical investigation

The electronic structure of the diatomic VO anion was explored by combining the photoelectron-imaging spectroscopy and high-level theoretical calculations. The electron affinity (EA) of VO is determined to be 1.244 \ifmmode\pm\else\textpm\fi{} 0.025 eV from the vibrationally resolved photoelectron spectrum acquired at 532 nm. The anisotropy parameter (\ensuremath{\beta}) for the EA defined peak is measured to be 1.59 \ifmmode\pm\else\textpm\fi{} 0.02, indicating that it is the 9\ensuremath{\sigma} electron attachment leading to the formation of the ground state of $\mathrm{V}{\mathrm{O}}^{\ensuremath{-}}$. The present imaging experiment provides direct evidence that the ground state of $\mathrm{V}{\mathrm{O}}^{\ensuremath{-}}$ is $X\phantom{\rule{0.16em}{0ex}}{}^{3}{\mathrm{\ensuremath{\Sigma}}}^{\ensuremath{-}}$ with a ${(3\ensuremath{\pi})}^{4}{(8\ensuremath{\sigma})}^{2}{(9\ensuremath{\sigma})}^{2}{(1\ensuremath{\delta})}^{2}$ electron configuration, which resolves the significant discrepancy in previous experiment and theory. In addition, the molecular orbitals and bonding involved in the anionic VO cluster are also examined based on the present high-level theoretical calculations.

High-resolution photoelectron imaging spectroscopy of cryogenically cooled Fe4O(-) and Fe5O(.).

We report high-resolution photodetachment spectra of the cryogenically cooled iron monoxide clusters Fe4O(-) and Fe5O(-) obtained with slow photoelectron velocity-map imaging (cryo-SEVI). Well-resolved vibrational progressions are observed in both sets of spectra, and transitions to low-lying excited states of both species are seen. In order to identify the structural isomers, electronic states, and vibrational modes that contribute to the cryo-SEVI spectra of these clusters, experimental results are compared with density functional theory calculations and Franck-Condon simulations. The main bands observed in the SEVI spectra are assigned to the (15)A2←(16)B2 photodetachment transition of Fe4O(-) and the (17)A'←(18)A″ photodetachment transition of Fe5O(-). We report electron affinities of 1.6980(3) eV for Fe4O and 1.8616(3) eV for Fe5O, although there is some uncertainty as to whether the (15)A2 state is the true ground state of Fe4O. The iron atoms have a distorted tetrahedral geometry in Fe4O(0/-) and a distorted trigonal-bipyramidal arrangement in Fe5O(0/-). For both neutral and anionic species, the oxygen atom preferably binds in a μ2-oxo configuration along the cluster edge. This finding is in contrast to prior predictions that Fe5O(0/-) exhibits a μ3 face-bound structure.

Long-lived coherence in pentafluorobenzene as a probe of ππ(*) - πσ(*) vibronic coupling.

The dynamics of pentafluorobenzene after femtosecond laser excitation to the optically bright ππ(*) first excited electronic state have been investigated by femtosecond time-resolved time-of-flight mass spectrometry and femtosecond time-resolved photoelectron imaging spectroscopy. The observed temporal profiles exhibit a bi-exponential decay behavior with a superimposed, long-lived, large-amplitude oscillation with a frequency of νosc = 78-74 cm(-1) and a damping time of τD = 5-2 ps. On the basis of electronic structure and quantum dynamics calculations, the oscillations have been shown to arise due to vibronic coupling between the optically bright ππ(*) state and the energetically close-lying optically dark πσ(*) state. The coupling leads to a pronounced double-well character of the lowest excited adiabatic potential energy surface along several out-of-plane modes of b1 symmetry. The optical electronic excitation initiates periodic wavepacket motion along these modes. In the out-of-plane distorted molecular configuration, the excited state acquires substantial πσ(*) character, thus modulating the ionization probability. The photoelectron spectra and the anisotropy of their angular distribution confirm the periodically changing electronic character. The ionizing probe laser pulse directly maps the coupled electron-nuclear motion into the observed signal oscillations.

Activation of Methane and Ethane as Mediated by the Triatomic Anion HNbN(-): Electronic Structure Similarity with a Pt Atom.

Investigations of the intrinsic properties of gas-phase transition metal nitride (TMN) ions represent one approach to gain a fundamental understanding of the active sites of TMN catalysts, the activities and electronic structures of which are known to be comparable to those of noble metal catalysts. Herein, we investigate the structures and reactivities of the triatomic anions HNbN(-) by means of mass spectrometry and photoelectron imaging spectroscopy, in conjunction with density functional theory calculations. The HNbN(-) anions are capable of activating CH4 and C2H6 through oxidative addition, exhibiting similar reactivities to free Pt atoms. The similar electronic structures of HNbN(-) and Pt, especially the active orbitals, are responsible for this resemblance. Compared to the inert NbN(-), the coordination of the H atom in HNbN(-) is indispensable. New insights into how to replace noble metals with TMNs may be derived from this combined experimental/computational study.