Rotational distributions following van der Waals molecule dissociation: Comparison between experiment and theory for benzene-Ar

Rebecca K. Sampson, Susan M. Bellm, Anthony J. McCaffery, and Warren D. Lawranc

A velocity map ion imaging study of difluorobenzene-water complexes: binding energies and recoil distributions

The binding energies of the p-, m-, and o-difluorobenzene-H2O complexes have been measured by velocity map ion imaging to be 922±10, 945±10, and 891±4 cm−1, respectively. The lack of variation provides circumstantial evidence for water binding to the three isomers via the same interaction, viz. an in-plane O–H⋯F hydrogen bond to one of the fluorine atoms on the ring, with a second, weaker interaction of the water O atom with an ortho hydrogen, as determined previously for the p-difluorobenzene-H2O complex. The ground state binding energies for the difluorobenzene-H2O complexes are ∼ 5%–11% larger than that for benzene-H2O, where binding occurs to the π electrons out-of-plane. However, in the S1 state the binding energies of the o- and p-difluorobenzene-H2O complexes are smaller than the benzene-H2O value, raising an interesting question about whether the geometry at the global energy minimum remains in-plane in the excited electronic states of these two complexes. Recoil energy distributions for dissociation of p-difluorobenzene-H2O have been measured from the 3 1, 5 2, and 3 1 5 1 levels of the excited electronic state. These levels are 490, 880, and 1304 cm−1, respectively, above the dissociation threshold. Within the experimental uncertainty, the recoil energy distributions are the same for dissociation from these three states, with average recoil energies of ∼ 100 cm−1. These recoil energies are 60% larger than was observed for the dissociation of p-difluorobenzene-Ar, which is a substantially smaller increase than the 400% seen in a comparable study of dissociation within the triplet state for pyrazine-Ar, -H2O complexes. The majority of the available energy is partitioned into vibration and rotation of the fragments

Elastic and inelastic cross sections for low-energy electron collisions with pyrimidine

We present theoretical elastic and electronic excitation cross sections and experimental electronic excitation cross sections for electron collisions with pyrimidine. We use the R-matrix method to determine elastic integral and differential cross sections and integral inelastic cross sections for energies up to 15 eV. The experimental inelastic cross sections have been determined in the 15–50 eV impact energy range. Typically, there is quite reasonable agreement between the theoretical and experimental integral inelastic cross sections. Calculated elastic cross sections agree very well with prior results

Experimental and theoretical cross sections for molecular-frame electron-impact excitation-ionization of D 2

We present both experimental and theoretical results for the dissociative ionization of D2 molecules induced by electron impact. Cross sections are determined in the molecular frame and are fully differential in the energies and emission angles of the di

Differential cross sections for the electron impact excitation of pyrimidine

We report on differential cross section (DCS) measurements for the electron-impact excitation of the electronic states of pyrimidine. The energy range of the present measurements was 15–50 eV with the angular range of the measurements being 10°–90°. All measured DCSs displayed forward-peaked angular distributions, consistent with the relatively large magnitudes for the dipole moment and dipole polarizability of pyrimidine. Excitations to triplet states were found to be particularly important in some energy loss features at the lower incident electron energies. To the best of our knowledge there are no other experimental data or theoretical computations against which we can compare the present results

Dynamical (e, 2e) Studies Using Tetrahydrofuran As a DNA Analog

Triple differential cross sections for the electron-impact ionization of the outer valence orbital of tetrahydrofuran have been measured using the (e, 2e) technique. The measurements have been performed with coplanar asymmetric kinematics, at an incident electron energy of 250 eV and at an ejected electron energy of 10 eV, over a range of momentum transfers. The experimental results are compared with theoretical calculations carried out using the molecular three-body distorted wave model. The results obtained are important for gaining an understanding of electron driven processes at a molecular level and for modeling energy deposition in living tissue

Experimental and Theoretical Cross Sections for Molecular-frame Electron-impact Excitation-ionization of D₂

We present both experimental and theoretical results for the dissociative ionization of D2 molecules induced by electron impact. Cross sections are determined in the molecular frame and are fully differential in the energies and emission angles of the dissociation fragments. Transitions are considered from the X1Σg+ electronic ground state of D2 to the 2sσg, 2pπu and 2pσu excited states of D2+. The experimental results are compared to calculations performed within the molecular four-body distorted-wave framework to describe the multicenter nature of the scattering process. The cross sections reveal a dramatic dependence on both the alignment of the internuclear axis with respect to the direction of the projectile momentum and on the symmetry of the excited dissociating state which is energetically resolved

Experimental and theoretical investigation of the triple differential cross section for electron impact ionization of pyrimidine molecules

Cross-section data for electron impact induced ionization of bio-molecules are important for modelling the deposition of energy within a biological medium and for gaining knowledge of electron driven processes at the molecular level. Triply differential cross sections have been measured for the electron impact ionization of the outer valence 7b2 and 10a1 orbitals of pyrimidine, using the (e, 2e) technique. The measurements have been performed with coplanar asymmetric kinematics, at an incident electron energy of 250 eV and ejected electron energy of 20 eV, for scattered electron angles of −5°, −10°, and −15°. The ejected electron angular range encompasses both the binary and recoil peaks in the triple differential cross section. Corresponding theoretical calculations have been performed using the molecular 3-body distorted wave model and are in reasonably good agreement with the present experiment

Ionization and Ionization-Excitation of Helium to the n=1-4 States of He⁺ by Electron Impact

We present experimental and theoretical results for the electron-impact-induced ionization of ground-state helium atoms. Using a high-sensitivity toroidal electron spectrometer, we measured cross-section ratios for transitions leading to the first three excited states of the residual helium ion relative to the transition leaving the ion in the ground state. Measurements were performed for both symmetric- and asymmetric-energy-sharing kinematics. By presenting results as a ratio, a direct comparison can be made between theoretical and experimental predictions without recourse to normalization. The experimental data are compared to theoretical predictions employing various first-order models and a second-order hybrid distorted-wave + convergent R matrix with pseudostates (close-coupling) approach. All the first-order models fail in predicting even the approximate size of the cross-section ratios. The second-order calculations are found to describe the experimental data for asymmetric-energy-sharing with reasonable fidelity, although significant disparities are evident for the symmetric-energy-sharing cases. These comparisons demonstrate the need for further theoretical developments, in which all four charged particles are treated on an equal footing

Dynamical (e, 2e) studies of tetrahydrofurfuryl alcohol

Cross section data for electron scattering from DNA are important for modelling radiation damage in biological systems. Triply differential cross sections for the electron impact ionization of the highest occupied outer valence orbital of tetrahydrofurfuryl alcohol, which can be considered as an analogue to the deoxyribose backbone molecule in DNA, have been measured using the (e,2e) technique. The measurements have been performed with coplanar asymmetric kinematics at an incident electron energy of 250 eV, an ejected electron energy of 20 eV, and at scattered electron angles of −5°, −10°, and −15°. Experimental results are compared with corresponding theoretical calculations performed using the molecular 3-body distorted wave model. Some important differences are observed between the experiment and calculations