Photoelectron Velocity-map Imaging Research Articles

Vibrational and electronic structure of the α- and β-naphthyl radicals via slow photoelectron velocity-map imaging.

Slow photoelectron velocity-map imaging (SEVI) spectroscopy has been used to study the vibronic structure of gas-phase α- and β-naphthyl radicals (C(10)H(7)). SEVI of cryogenically cooled anions yields spectra with <4 cm(-1) resolution, allowing for the observation and interpretation of congested vibrational structure. Isomer-specific photoelectron spectra of detachment to the radical ground electronic states show detailed structure, allowing assignment of vibrational fundamental frequencies. Transitions to the first excited states of both radical isomers are also observed; vibronic coupling and photodetachment threshold effects are considered to explain the structure of the excited bands.

Removing electrons from more than one orbital: direct and indirect pathways to excited states of molecular cations

We use velocity map imaging of photoelectrons in coincidence with molecular cations to determine which ionic states are populated via strong field ionization, and whether the ionization to excited ionic states proceeds indirectly via the ground ionic state or directly from the neutral. We carry out measurements on a series of molecules that have different energy gaps between the ground ionic state and dissociative excited states. We measure both direct and indirect ionization to excited states of the molecular cations, and find that the energy gap between non-dissociative and dissociative states plays an important role in determining the amount of excited state ionization. Direct ionization to dissociative states is generally comparable to ionization to the ground state for gap energies less than the photon energy, but is suppressed for gap energies larger than the photon energy.

Structural evolution of homoleptic heterodinuclear copper-nickel carbonyl anions revealed using photoelectron velocity-map imaging.

The homoleptic heterodinuclear copper-nickel carbonyl anions CuNi(CO)n(-) (n = 2-4) were generated in a pulsed-laser vaporization source and investigated using photoelectron velocity-map imaging spectroscopy. The electron affinities of CuNi(CO)2 (2.15 ± 0.03 eV), CuNi(CO)3 (2.30 ± 0.03 eV), and CuNi(CO)4 (1.90 ± 0.04 eV) were deduced from the photoelectron spectra. Theoretical calculations at the B3LYP level were carried out to elucidate the structures and the electronic properties of CuNi(CO)n(0/1-) (n = 1-4) and to support the experimental observations. Comprehensive comparisons between experiments and calculations suggest that there is a turnover point of the absorption site during the progressive carbonylation process. The carbonyl groups are determined to be preferentially bonded to the nickel atom. When the nickel center satisfies the 18-electron configuration, the copper atom starts to adsorb additional CO molecules. These results will shed light on the bonding mechanisms of the heterometallic carbonyl clusters.

Ultrafast dynamics of ethylbenzene cations probed by photofragmentation and photoelectron spectrometry

Ultrafast dynamics of ethylbenzene (EB) cation has been studied by time-resolved photofragmentation mass-spectrometry (PFMS) in combination with photoelectron spectrometry. EB cations were prepared by multiphoton ionization. The photoelectron spectrum was registered by photoelectron velocity map imaging (PEVMI) and the observed bands were assigned to different cation states. The ultrafast dynamics of these cation states are measured by monitoring the time dependent parent-ion depletion and the fragment-ion appearance, simultaneously. An ultrafast relaxation time of the parent ion of 2.50 (±0.13) ps has been inferred, which is attributed to a dissipative intramolecular vibrational redistribution (IVR) process within the D0 cation state. The results were compared with o-xylene cations, an isomer of EB.

Structural isomers of Ti₂O₄ and Zr₂O₄ anions identified by slow photoelectron velocity-map imaging spectroscopy.

High-resolution anion photoelectron spectra are reported for the group 4 metal dioxide clusters Ti2O4(-) and Zr2O4(-). Slow photoelectron velocity-map imaging (SEVI) spectroscopy of cryogenically cooled, mass-selected anions yields photoelectron spectra with submillielectronvolt resolution, revealing extensive and well-resolved vibrational progressions. By comparison of the spectra with Franck-Condon simulations, we have identified the C(2v) and C(3v) isomers as the ground states of Ti2O4(-) and Zr2O4(-) anions, respectively. Minor contributions from the C(2h) isomer of Ti2O4(-) and the C(2v) isomer of Zr2O4(-) are also seen. The SEVI spectra yield upper bounds for the adiabatic detachment energies, as well as vibrational frequencies for various modes of the neutral Ti2O4 and Zr2O4 species.

Photoelectron holography in strong optical and dc electric fields

The application of velocity map imaging for the detection of photoelectrons resulting from atomic or molecular ionization allows the observation of interferometric, and in some cases holographic structures that contain detailed information on the target from which the photoelecrons are extracted. In this contribution we present three recent examples of the use of photoelectron velocity map imaging in experiments where atoms are exposed to strong optical and dc electric fields. We discuss (i) observations of the nodal structure of Stark states of hydrogen measured in a dc electric field, (ii) mid-infrared strong-field ionization of metastable Xe atoms and (iii) the reconstruction of helium electronic wavepackets in an attosecond pump-probe experiment. In each case, the interference between direct and indirect electron pathways, reminiscent of the reference and signal waves in holography, is seen to play an important role.

Rovibronic structure in slow photoelectron velocity-map imaging spectroscopy of CH2CN− and CD2CN−

We report high-resolution anion photoelectron spectra of the cryogenically cooled cyanomethide anion, CH2CN(-), and its isotopologue, CD2CN(-), using slow photoelectron velocity-map imaging (SEVI) spectroscopy. Electron affinities of 12 468(2) cm(-1) for CH2CN and 12 402(2) cm(-1) for CD2CN are obtained, demonstrating greater precision than previous experiments. New vibrational structure is resolved for both neutral species, especially activity of the ν5 hydrogen umbrella modes. The ν6 out-of-plane bending mode fundamental frequency is measured for the first time in both systems and found to be 420(10) cm(-1) for CH2CN and 389(8) cm(-1) for CD2CN. Some rotational structure is resolved, allowing for accurate extraction of vibrational frequencies. Temperature-dependent SEVI spectra show marked effects ascribed to controlled population of low-lying anion vibrational levels. We directly measure the inversion splitting between the first two vibrational levels of the anion ν5 umbrella mode in both species, finding a splitting of 130(20) cm(-1) for CH2CN(-) and 81(20) cm(-1) for CD2CN(-). Franck-Condon forbidden activity is observed and attributed to mode-specific vibrational autodetachment from the CH2CN(-) and CD2CN(-) dipole bound excited states. We also refine the binding energy of the anion dipole bound states to 39 and 42 cm(-1), respectively, for CH2CN(-) and CD2CN(-).

Vibrationally Resolved Photoelectron Imaging of Au3H–

We report a combined photoelectron velocity map imaging spectroscopy and density functional theory investigation on the Au3H(-) anion. Transition between the anionic electronic ground state and the neutral electronic ground state is revealed. Vibrationally resolved spectra were recorded at two different photon energies, providing a wealth of spectroscopic information for the electronic ground state of the Au3H. Franck-Condon simulations of the ground-state transition are carried out to assist in the assignment of the vibrationally resolved spectra. The electron affinity and vertical detachment energy of Au3H are measured to be 2.548 ± 0.001 and 2.570 ± 0.001 eV, respectively. Three stretching vibrational modes are determined to be activated upon photodetachment, with the frequencies of 2100 ± 100, 177 ± 10, and 96 ± 10 cm(-1).

On the photoelectron velocity-map imaging of lutetium monoxide anion LuO−

We report a combined photoelectron velocity-map imaging spectroscopy and density functional theory investigation on lutetium monoxide anion. Transition between the X (1)Σ(+) anion electronic ground state and the neutral X (2)Σ(+) electronic ground state is observed. Vibrationally resolved spectra were obtained at four different photon energies, providing a wealth of spectroscopic information for the electronic ground states of the anionic lutetium monoxide and corresponding neutral species. Franck-Condon simulations of the ground-state transition are performed to assign vibrational structure in the spectra and to assist in identifying the observed spectral bands. The electronic ground state of LuO(-) is found to have a vibrational frequency of 743 ± 10 cm(-1) and an equilibrium bond length of 1.841 Å. The electron affinity of LuO is measured to be 1.624 ± 0.002 eV. The fundamental frequency of ground-state LuO is estimated to be 839 ± 10 cm(-1).

Vibronic structure of VO2 probed by slow photoelectron velocity-map imaging spectroscopy.

We report high-resolution anion photoelectron spectra of vanadium dioxide (VO2 (-)) obtained by slow electron velocity-map imaging of trapped and cryogenically cooled anions. Vibrationally resolved spectra are obtained for photodetachment to the first three neutral electronic states, giving an electron affinity of 1.8357(5) eV for the X̃A12 ground state and term energies of 0.1845(8) eV and 0.8130(5) eV for the ÃB12 and B̃A12 excited states, respectively. The vibrational fundamentals ν1 and ν2 are obtained for all three states. Experimental assignments are confirmed by energies from electronic structure calculations and Franck-Condon spectral simulations. These simulations support assigning the anion ground state as the X̃B13 state. With this assignment, photodetachment to the B̃A12 state involves a nominally forbidden two-electron transition, suggesting extensive configuration interaction in neutral VO2.

Hydrogen bonding in microsolvation: photoelectron imaging and theoretical studies on Aux−–(H2O)n and Aux−–(CH3OH)n (x = 1, 2; n = 1, 2) complexes

We have combined photoelectron velocity-map imaging (VMI) spectroscopy and theoretical calculations to elucidate the geometry and energy properties of Aux(-)(Solv)n clusters with x = 1, 2; n = 1, 2; and Solv = H2O and CH3OH. Besides the blue-shifted vertical electron detachment energies (VDEs) of the complexes Au1,2(-)(Solv)n with the increase of the solvation number (n), we independently probed two distinct Au(-)(CH3OH)2 isomers, which combined with MP2/aug-cc-pVTZ(pp) calculations represent a competition between O···H-O hydrogen bonds (HBs) and Au···H-O nonconventional hydrogen bonds (NHBs). Complementary calculations provide the total binding energies of the low-energy isomers. Moreover, the relationship between the total binding energies and total VDEshift is discussed. We found that the Au1,2(-) anions exhibit halide-analogous behavior in microsolvation. These findings also demonstrate that photoelectron velocity map imaging spectroscopy with the aid of the ab initio calculations is an effective tool for investigating weak-interaction complexes.

Design Near-threshold Photoelectron Imaging Spectrometer Based on UV Laser Induced Photoelectron Emission Anion Source

We have developed a compact photoelectron imaging facility, including an anion source with dissociative photoelectron attachment to molecules, a linear time-of-flight mass spectrometry (TOFMS), and an orthogonal high-resolution threshold photoelectron velocity map imaging spectrometer (VMI). Intense and cold cluster anions were prepared in photoelectron-attachment processes upon pulsed UV laser ablation of metal target. Combining this anion source with TOFMS-VMI, the achieved mass resolution is about 200, and the electron kinetic energy resolution is better than 3%, i.e., 30 meV for 1 eV electrons. More importantly, low-energy photoelectron imaging spectra for CH3S− and S2− at 611.46 nm are obtained. In both cases, the refined electron affinities are determined to be 1.8626±0.0020 eV for CH3S and 1.6744±0.0035 eV for S2, respectively. Preliminary results suggest that the apparatus is a powerful tool for estimating precise electron affinities values from threshold photoelectron imaging spectroscopy.

Femtosecond Photodetachment of Silver Anions

The two- and three-photon detachment of negative silver ions in a femtosecond infrared laser field is studied using photoelectron velocity map imaging methods. Photoelectron angular distributions (PADs) are obtained for these detachment channels; these PADs change dramatically when the laser wavelength and intensity are changed. Theoretical predictions, which are based on the adiabatic Keldysh-Faisal-Reiss saddle point method, are in good agreement with our experiment. The dependence of the PAD on the laser wavelengths and intensities is due to the interference between the different partial wave functions. The relative contributions of the different partial waves to the detachment amplitude are altered by changing the laser parameters and, as a result, the shape of the PAD. Close to the detachment threshold, the two-photon detachment process also follows the Wigner threshold law. Near the detachment threshold, the large differences between the calculated results and our experimental results indicate that the ponderomotive energy shifts caused by the femtosecond laser fields must be taken into account in the theoretical model. The three-photon detachment of Ag(-) is also observed and compared with theoretical calculations.

Vibrational fine structure of C5 via anion slow photoelectron velocity-map imaging

High-resolution anion photoelectron spectra of cryogenically cooled C5(-) clusters are reported using slow photoelectron velocity-map imaging spectroscopy. We resolve vibronic transitions to the ν2 stretching mode and multiply excited ν5, ν6, and ν7 bending modes of neutral C5 with significantly higher accuracy than previous experiments. Weak transitions to Franck-Condon (FC) forbidden singly excited bending modes are made possible by Herzberg-Teller coupling between electronic states of the neutral cluster. In addition, we resolve vibrational fine structure corresponding to different angular momentum states of multiply excited bending modes. The observation of this multiplet structure, some of which is FC forbidden, is attributed to Renner-Teller coupling between vibrational levels in the C5(-) ground electronic state.

Comment on “Photoelectron angular distributions as a probe of alignment in a polyatomic molecule: Picosecond time- and angle-resolved photoelectron spectroscopy of S1 p-difluorobenzene” [J. Chem. Phys. 111, 1438 (1999)

In this Comment we submit the results of an experiment in which we use the technique of time-resolved photoelectron velocity map imaging to probe the intramolecular dynamics occurring following the preparation of the 3151 vibrational level in S1 p-difluorobenzene with a 1 ps laser pulse. The extracted photoelectron angular distributions are discussed in the context of earlier comparable measurements from our group [J. Chem. Phys. 111, 1438 (1999)], and we conclude that the specific interpretation of the earlier results was incorrect as a consequence of systematic errors that are removed in the present study.

Structure of Au40/−1 in the gas phase: A joint geometry relaxed ab initio calculations and vibrationally resolved photoelectron imaging investigation

We have combined photoelectron velocity-map imaging spectroscopy and high-level ab initio calculations to elucidate the geometries of Au4 (0/-1). Well-resolved ground-state electronic transition was observed in the photoelectron spectrum of Au4 (-) at 446 nm, leading to more accurate electron affinity and vibrational frequencies for the ground state of the neutral Au4 (-). The pure and vibrationally resolved spectra provide definitive experimental evidence for the resolution of the ground-state gold tetramer in the gaseous phase, with the aid of the ab initio calculations and Franck-Condon simulations. The comprehensive comparisons between the experiment and theoretical calculations suggest that the Y-shaped structure is the global minimum for both the neutral and anionic Au4.

Photoelectron velocity-map imaging spectroscopic and theoretical study on the reactivity of the gold atom toward CH3SH, CH3OH, and H2O

Photoelectron velocity-map imaging spectroscopy has been used to study the reaction of the anionic gold atom with the HR (R = SCH3, OCH3, OH) molecules. The solvated [Au···HR](-) and inserted [HAuR](-) products have been experimentally observed for R = SCH3, whereas only solvated [Au⋯HR](-) products were found for R = OCH3 and OH. This significant difference in the photoelectron spectra suggests the different reactivity of the Au(-) toward the CH3SH, CH3OH, and H2O molecules. Second order Møller-Plesset perturbation theory and coupled-cluster single double triple excitation calculations have been performed to aid the structural assignment of the spectra and to explore the reaction mechanism. Activation energies for the isomerizations of the solvated structures to the inserted ones in the Au(-)∕Au + HR reactions (R = OCH3 and OH) are predicted to be much higher than those for the Au(-)∕Au + CH3SH reactions, supporting the experimental observation. Theoretical calculations provide the evidence that the intriguing [HAuSCH3](-) product may be formed by the attachment of the electron onto the neutral HAuSCH3 species or the isomerization from the anionic [Au···HSCH3](-) one. These findings should be helpful for understanding the feature that the thiols are able to form the staple motifs, whereas CH3OH and H2O are not.

Slow photoelectron velocity-map imaging spectroscopy of cold negative ions

Anion slow photoelectron velocity-map imaging (SEVI) spectroscopy is a high-resolution variant of photoelectron spectroscopy used to study the electronic and geometric structure of atoms, molecules, and clusters. To benefit from the high resolution of SEVI when it is applied to molecular species, it is essential to reduce the internal temperature of the ions as much as possible. Here, we describe an experimental setup that combines a radio-frequency ion trap to store and cool ions with the high-resolution SEVI spectrometer. For C(5)(-), we demonstrate ion temperatures down to 10 ± 2 K after extraction from the trap, as measured by the relative populations of the two anion spin-orbit states. Vibrational hot bands and sequence bands are completely suppressed, and peak widths as narrow as 4 cm(-1) are seen due to cooling of the rotational degrees of freedom.

Vibrationally resolved photoelectron imaging of platinum carbonyl anion Pt(CO)n− (n = 1-3): Experiment and theory

Photodetachment of platinum carbonyl anions Pt(CO)(n)(-) (n = 1, 3) had been previously investigated using traditional photoelectron spectroscopy (PES) [G. S. Icking-Konert, H. Handschuh, G. Ganteför, and W. Eberhardt, Phys. Rev. Lett. 76, 1047 (1996); B. Chatterjee, F. A. Akin, C. C. Jarrold, and K. Raghavachari, J. Chem. Phys. 119, 10591 (2003)]. Here, we studied Pt(CO)(n)(-) (n = 1-3) using photoelectron velocity-map imaging method and extensive theoretical calculations. Vibrationally resolved spectra from photoelectron imaging experiments allow determination of the electron affinities of Pt(CO)(n), which are 1.196 ± 0.034, 0.930 ± 0.042, and 1.253 ± 0.032 eV for n = 1, 2, and 3, respectively. Two vibrational progressions are resolved for the ground states of Pt(CO) and Pt(CO)(3), while only one is resolved for that of Pt(CO)(2). The frequencies are determined to be 2089 ± 91 and 581 ± 21 cm(-1) for Pt(CO), 2173 ± 115 cm(-1) for Pt(CO)(2) and 2119 ± 88 and 444 ± 18 cm(-1) for Pt(CO)(3). Results from density functional theory and ab initio calculations agreed well with the experimental observations. The spectra were well reproduced by Franck-Condon fitting on the basis of the optimized geometries and the theoretical frequencies. The well-resolved PES also provided valuable benchmarks for various density functionals (B3LYP, BP86, and PW91PW91) for the platinum carbonyls.

Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions

A set of silver-doped lead Zintl anions, Ag@Pb(n)(-) (n = 5-12), have been studied using photoelectron velocity-map imaging spectroscopy and quantum chemical calculation. The structures of Ag@Pb(n)(-) (n = 7-9, 11) built upon a square pyramid base, hitherto not considered, were assigned. Overall agreement between the experimental and calculated photoelectron spectra as well as vertical detachment energies allows for structural evolution to be established. The silver atom prefers to stay outside in the n ≤ 6 clusters and intends to be encapsulated by the lead atoms in n > 6. A stable endohedral cage with bicapped square antiprism structure is formed at n = 10, the endohedral structure of which persists for the larger clusters. Especially, these Ag@Pb(n)(-) anions have been found to undergo a transition between square pyramid and pentagonal pyramid molecular structures at n = 11.