Yaguo Tang

Momentum imaging spectrometer for molecular fragmentation dynamics induced by pulsed electron beam

A momentum imaging spectrometer has been built for studying the electron impact molecular fragmentation dynamics. The setup consists of a pulsed electron gun and a time of flight system as well as a two-dimensional time and position sensitive multi-hit detector. The charged fragments with kinetic energy up to 10 eV can be detected in 4π solid angles and their three-dimensional momentum vectors can be reconstructed. The apparatus is tested by electron impact ionization of Ar and dissociative ionization of CO2. By analyzing the ion-ion coincidence spectra, the complete and incomplete Coulomb fragmentation channels for CO2(2+) and CO2(3+) are identified. The kinetic energy release (KER) and angular correlation for the two-body breakup channel CO2(2+*) → O(+) + CO(+) are reported. The peak value of total KER is found to be 6.8 eV which is consistent with the previous photoion-photoion coincidence studies, and the correlation angle of O(+) and CO(+) is also explicitly determined to be 172.5°.

Vibrational Effects on Electron Momentum Distributions of Outer-Valence Orbitals of Oxetane

Vibrational effects on electron momentum distributions (EMDs) of outer-valence orbitals of oxetane are computed with a comprehensive consideration of all vibrational modes. It is found that vibrational motions influence EMDs of all outer-valence orbitals noticeably. The agreement between theoretical and experimental momentum profiles of the first five orbitals is greatly improved when including molecular vibrations in the calculation. In particular, the large turn-up at low momentum in the experimental momentum profile of the 3b1 orbital is well interpreted by vibrational effects, indicating that, besides the low-frequency ring-puckering mode, C-H stretching motion also plays a significant role in affecting EMDs of outer-valence orbitals of oxetane. The case of oxetane exhibits the significance of checking vibrational effects when performing electron momentum spectroscopy measurements.

Electron Momentum Spectroscopy Investigation of Molecular Conformations of Ethanol Considering Vibrational Effects

The interpretation of experimental electron momentum distributions (EMDs) of ethanol, one of the simplest molecules having conformers, has confused researchers for years. High-level calculations of Dyson orbital EMDs by thermally averaging the gauche and trans conformers as well as molecular dynamical simulations failed to quantitatively reproduce the experiments for some of the outer valence orbitals. In this work, the valence shell electron binding energy spectrum and EMDs of ethanol are revisited by the high-sensitivity electron momentum spectrometer employing symmetric noncoplanar geometry at an incident energy of 1200 eV plus binding energy, together with a detailed analysis of the influence of vibrational motions on the EMDs for the two conformers employing a harmonic analytical quantum mechanical (HAQM) approach by taking into account all of the vibrational modes. The significant discrepancies between theories and experiments in previous works have now been interpreted quantitatively, indicating that the vibrational effect plays a significant role in reproducing the experimental results, not only through the low-frequency OH and CH3 torsion modes but also through other high-frequency ones. Rational explanation of experimental momentum profiles provides solid evidence that the trans conformer is slightly more stable than the gauche conformer, in accordance with thermodynamic predictions and other experiments. The case of ethanol demonstrates the significance of considering vibrational effects when performing a conformational study on flexible molecules using electron momentum spectroscopy.

Imaging molecular geometry with electron momentum spectroscopy

Electron momentum spectroscopy is a unique tool for imaging orbital-specific electron density of molecule in momentum space. However, the molecular geometry information is usually veiled due to the single-centered character of momentum space wavefunction of molecular orbital (MO). Here we demonstrate the retrieval of interatomic distances from the multicenter interference effect revealed in the ratios of electron momentum profiles between two MOs with symmetric and anti-symmetric characters. A very sensitive dependence of the oscillation period on interatomic distance is observed, which is used to determine F-F distance in CF4 and O-O distance in CO2 with sub-Ångström precision. Thus, using one spectrometer, and in one measurement, the electron density distributions of MOs and the molecular geometry information can be obtained simultaneously. Our approach provides a new robust tool for imaging molecules with high precision and has potential to apply to ultrafast imaging of molecular dynamics if combined with ultrashort electron pulses in the future.

Note: A high-efficiency multi-coincidence method designed for molecular fragmentation studies

A high-efficiency multi-coincidence method is developed based on the hardware electronic multiple coincidence units. The multi-hit signals originating from one single detector can be selected and measured in coincidence. The performance of the method is tested by the electron impact three-body fragmentation of CO2(3+). Compared to the conventional method, the relative and absolute coincidence efficiencies of the triple-coincidence measurement are improved by about 200 and 3 times, respectively.

Time-resolved (e, 2e) electron momentum spectroscopy on the toluene S1 excited state

We report a time-resolved (e, 2e) experiment on the toluene molecule in the S1(π, π*) state. The toluene S1 state was prepared by a 267 nm pump laser and probed with electron momentum spectroscopy using a 1.2 keV incident electron beam consisting of a train of 4 or 8 ultrashort electron pulses (~ 1 ps) with 0.3 or 0.7 ns intervals. In spite of the low data statistics, the experimental results clearly demonstrate that the present technique selectively probes ionization transition to two-hole-one-particle configurations that are hardly accessible from the ground electronic state.

Development of an electron momentum spectrometer for time-resolved experiments employing nanosecond pulsed electron beam

The low count rate of (e, 2e) electron momentum spectroscopy (EMS) has long been a major limitation of its application to the investigation of molecular dynamics. Here we report a new EMS apparatus developed for time-resolved experiments in the nanosecond time scale, in which a double toroidal energy analyzer is utilized to improve the sensitivity of the spectrometer and a nanosecond pulsed electron gun with a repetition rate of 10 kHz is used to obtain an average beam current up to nA. Meanwhile, a picosecond ultraviolet laser with a repetition rate of 5 kHz is introduced to pump the sample target. The time zero is determined by photoionizing the target using a pump laser and monitoring the change of the electron beam current with time delay between the laser pulse and electron pulse, which is influenced by the plasma induced by the photoionization. The performance of the spectrometer is demonstrated by the EMS measurement on argon using a pulsed electron beam, illustrating the potential abilities of the apparatus for investigating the molecular dynamics in excited states when employing the pump-probe scheme.

Development of multi-channel apparatus for electron-atom Compton scattering to study the momentum distribution of atoms in a molecule

We have developed multi-channel apparatus for electron-atom Compton scattering to study the momentum distribution of atoms in a molecule. It combines the features of both a spherical electron energy analyzer and a large-area position sensitive detector, thereby having an ability to cover almost completely the azimuthal angle range available for quasi-elastic electron Rutherford backscattering at an angle of 135°. Details and performance of the apparatus are reported, together with experimental results measured for Xe and CH4 at an incident electron energy of 2 keV. In particular, it is shown that the instrumental sensitivity is remarkably high, which has increased the signal count rate by nearly three orders of magnitude compared to existing setups. This technical progress would be useful for advancing atomic momentum spectroscopy studies.

Multi-center interference effect on (e, 2e) electron momentum spectroscopy

The multi-center interference effect of three outermost molecular orbitals (MOs) of CF4 is investigated using (e, 2e) electron momentum spectroscopy. We show that the observed oscillations are directly informative of the nature of molecular structure. By fitting the experimental results, the bond length of F-F of gas phase CF4 is determined.

Three-body fragmentation dynamics of CO2q+ (q = 3, 4) induced by electron collision at 500 eV impact energy

Electron impact induced three-body fragmentation of CO2q+ (q = 3, 4) is investigated. For CO23+, non-sequential and sequential fragmentation processes are observed. For CO4+2, however, only non-sequential fragmentation processes are observed. The momentum correlations of each dissociative channel is analyzed by Newton diagram.