Search

A joint experimental and theoretical investigation of the valence shell excitations of carbon tetrachloride has been performed by fast electron scattering and time dependent density functional theory calculations. At a collision energy of 1.5 keV and an energy resolution of about 70 meV, the dipole-forbidden transition of a

The oscillator strengths and integral cross sections of the valence-shell excitations of HCl have significant applications in the studies of planetary atmospheres and interstellar gases. In the present work, the generalized oscillator strengths of the valence-shell excitations of HCl have been measured at an incident electron energy of 1500 eV and an energy resolution of 70 meV, and their momentum transfer dependence behaviors have been elucidated. It is observed that the generalized oscillator strength ratios of the b3Π1(ν' = 0) state to the C1Π(ν' = 0) state are a constant and independent of the squared momentum transfer, and this typical behavior in the momentum space is explained by the intraconfiguration mixing of the b3Π1 and C1Π states due to the spin-orbital interaction. The optical oscillator strengths of the valence-shell excitations have been obtained by extrapolating the generalized oscillator strengths to the limit of zero squared momentum transfer. The present optical oscillator strengths give an independent cross-check to the previous experimental and theoretical results, and it is found that most of the photoabsorption measurements are limited by the line saturation effect. The integral cross sections of the valence-shell excitations of HCl have been obtained systematically from the threshold to 5000 eV with the aid of the BE-scaling method.

The dispute about whether the 1s core-hole is localized on one atom or delocalized over both in a homonuclear diatomic molecule has continued for decades, which has been extensively studied by the photoelectron and electron–ion coincidence spectroscopies. For N2, if the 1s core-hole is delocalized, the K-shell excitation into the 1π g orbital should split into two components, i.e., the dipole-allowed transition from the ungerade 1σ u state and the dipole-forbidden transition from the gerade 1σ g state. However, only the dipole-allowed transition has been observed up to now. Here, we report the inner-shell electron energy loss spectra of N2 at different scattering angles with an incident electron energy of 1500 eV and an energy resolution of 65 meV. The vibrational structures of both the dipole-allowed ( 1 s σ u ) − 1 ( 1 π g ) 1 and dipole-forbidden ( 1 s σ g ) − 1 ( 1 π g ) 1 states of N2 have been identified at different momentum transfers. The splitting between the ( 1 σ g ) − 1 ( 1 π g ) 1 and ( 1 σ u ) − 1 ( 1 π g ) 1 states with the reverse symmetry is determined to be 67 ± 7 meV. Moreover, the momentum transfer dependence behavior of the transition intensity ratio agrees with the theoretical predictions, as increasing to a maximum and then decreasing. The experimental observations clearly show that the inner most electrons can be described by 1σ g and 1σ u , which indicates that the inner-shell 1s core-hole of N2 is delocalized over two N atoms based on the excitation process.

The oscillator strengths of the valence–shell excitations of C2H2 are extremely important for testing theoretical models and studying interstellar gases. In this study, the high-resolution inelastic x-ray scattering (IXS) method is adopted to determine the generalized oscillator strengths (GOSs) of the valence–shell excitations of C2H2 at a photon energy of 10 keV. The GOSs are extrapolated to their zero limit to obtain the corresponding optical oscillator strengths (OOSs). Through taking a completely different experimental method of the IXS, the present results offer the high energy limit for electron collision to satisfy the first Born approximation (FBA) and cross-check the previous experimental and theoretical results independently. The comparisons indicate that an electron collision energy of 1500 eV is not enough for C2H2 to satisfy the FBA for the large squared momentum transfer, and the line saturation effect limits the accuracy of the OOSs measured by the photoabsorption method.

Trifluoromethane is an important etching gas in semiconductor industries as the fluorine source in reactive etching plasma. Electron impact excitations into the dissociation states are essential for plasma modeling. By employing an angle-resolved electron energy loss spectrometer, the generalized oscillator strengths (GOSs) for the valence-shell excited states have been determined at an absolute scale utilizing the crossed-beam based relative flow technique. The measurement was performed with an incident electron energy of 1500 eV at an energy resolution of about 70 meV. The corresponding optical oscillator strengths are also obtained by extrapolating the measured GOSs to the limit of zero momentum transfer. The extrapolated data and fitted linewidths are used to reproduce the photoabsorption spectra and compare with the available experimental and theoretical results. In addition, the integral cross sections from the excitation threshold to 5000 eV of the associated excited states have been derived by using the BE-scaling method. The resulted data can not only be used in plasma models but also serve as a benchmark for further theoretical calculations.

Understanding the role of inelastic electron scattering in water is of fundamental importance in various fields ranging from atmospheric chemistry to radiation biology. The lack of accurate excitation cross sections for water results in a large uncertainty, for example, in the track structure simulation for modeling radiation damage to DNA. The large differences of the integral cross sections (ICSs) for the optical-allowed excitations ${\stackrel{\ifmmode \tilde{}\else \~{}\fi{}}{A}}^{1}{B}_{1}$ and ${\stackrel{\ifmmode \tilde{}\else \~{}\fi{}}{B}}^{1}{A}_{1}$ of ${\mathrm{H}}_{2}\mathrm{O}$ among experiments and theories have been maintaining for decades. To resolve this issue, by combining the ab initio calculation with the electron correlation being taken into account accurately, we compare the ICSs determined by high-energy electron scattering with the existing experiments at low and intermediate energies and theories, where the present experiment eliminated the errors from the spectral deconvolution in low-energy measurements. Our work provides a recommendation for the ICSs of the two excitations from thresholds up to several keV, and suggests the existing selected ICSs for ${\mathrm{H}}_{2}\mathrm{O}$ be revised for accurate modeling radiation effects in biological matter and describing the transport properties of electrons in aqueous systems.

The valence-shell excitations of hydrogen sulfide have been studied by fast electron impact at a collision energy of 1.5 keV and an energy resolution of about 70 meV. By analyzing the variations of intensity and shape of the feature in the range of 5.0-7.5 eV at different scattering angles, the excitation energy of 5.85 ± 0.01 eV and the line width of 0.80 ± 0.01 eV of the 3b21A2 state have been determined. The generalized oscillator strengths of the valence-shell excitations in the energy range of 5.0-9.2 eV of hydrogen sulfide have been determined from the measured spectra. The corresponding optical oscillator strengths have been obtained by extrapolating the generalized oscillator strengths to the limit of zero squared momentum transfer. The integral cross sections have also been systematically determined from the threshold to 5000 eV by means of the BE-scaling method. The presently obtained oscillator strengths and integral cross sections have significant applications in the studies of planetary atmospheres and interstellar gases.

The vibrationally resolved generalized oscillator strengths of the first and strongest singlet excitation ÃA2″1← X̃

The generalized oscillator strengths of the valence-shell excitations from the ground state to 3p5(4s, 4s', 4p, 4p', 3d, 3d', 5p, 5p', 5s, 4d) of argon have been determined at an incident electron energy of 1500 eV and an energy resolution about 90 meV. The accuracy of the present generalized oscillator strengths is improved by the adopted relative flow technique. The comprehensive comparison of the present results with the previous experimental and theoretical ones shows that the first Born approximation is satisfied in the lower squared momentum transfer region for the electric dipole excitations, while the deviations from the prediction of the first Born approximation and the inelastic X-ray scattering measurements near the minimum and in the larger K2 region are obvious, which can be attributed to the failure of the first Born approximation in this K2 region. The invalidity of the first Born approximation has also been observed for the electric monopole transitions even at a high impact electron energy of 2500 eV.

The vibrationally resolved generalized oscillator strengths of the first and strongest singlet excitation AA2″1← X1A1 of ammonia have been determined at an impact electron energy of 1500 eV with an energy resolution of 80 meV. The comprehensive comparison of the present results with the previous experimental and theoretical ones shows that the high-energy limit, where the first Born approximation holds, has been reached at an impact electron energy of 1500 eV in K2 1 a.u. even at 1500 eV. It is also observed that the minimum position of the generalized oscillator strength of the vibronic state shifts toward the larger squared momentum transfer with the increasing vibrational quantum number. By extrapolating the generalized oscillator strength to the zero momentum transfer, the optical oscillator strength of the AA2″1 state has been obtained, which gives an independent cross check to the previous results. The integral cross sections of the AA2″1 state have been obtained systematically from the threshold to 5000 eV with the aid of the BE-scaling method.