Improved theoretical calculations for electron-impact ionization of DNA analogue molecules.

Ionizing interactions between charged particles and molecules of biological relevance have attracted considerable interest in the last decade due to its importance in medical radiation therapy. We have previously calculated triply differential cross sections for five biomolecules in collaboration with experimental groups. We used the molecular 3-body distorted wave approximation for these calculations. For ionization of biomolecules, experimentalists are unable to determine the orientation of the molecule at the time of ionization, which means that the calculated cross sections need to be averaged over all molecular orientations. At the time the calculations were performed, it was not numerically feasible for us to perform proper averaging over orientations, so we introduced the orientation averaged molecular orbital approximation to make the calculations possible. We now have the computational capability to properly perform this average, so, here, we present new results with a proper average over orientations and compare with the previous calculations and experiment. Since the original calculations, results from two different distorted-wave models have also been published and the new results will also be compared with those calculations. Overall, the new results are in better agreement with the experiment.

A dynamical (e,2e) investigation into the ionization of the outermost orbitals of R-carvone.

We report an experimental and theoretical investigation into the dynamics of electron-impact ionization of R-carvone. Experimental triple differential cross sections are obtained in asymmetric coplanar kinematic conditions for the ionization of the unresolved combination of the three outermost molecular orbitals (41a-39a) of R-carvone. These cross sections are compared with theoretical cross sections calculated within a molecular 3-body distorted wave (M3DW) framework employing either a proper orientation average or orbital average to account for the random orientation of the molecule probed in the experiment. Here, we observe that the overall scattering behavior observed in the experiment is fairly well reproduced within the M3DW framework when implementing the proper average over orientations. The character of the ionized orbitals also provides some qualitative explanation for the observed scattering behavior. This represents substantial progress when trying to describe the scattering dynamics observed for larger molecules under intermediate-impact energy and asymmetric energy sharing scattering conditions.

Electron impact ionization dynamics of para-benzoquinone.

Triple differential cross sections (TDCSs) for the electron impact ionization of the unresolved combination of the 4 highest occupied molecular orbitals (4b3g, 5b2u, 1b1g, and 2b3u) of para-benzoquinone are reported. These were obtained in an asymmetric coplanar geometry with the scattered electron being observed at the angles -7.5°, -10.0°, -12.5° and -15.0°. The experimental cross sections are compared to theoretical calculations performed at the molecular 3-body distorted wave level, with a marginal level of agreement between them being found. The character of the ionized orbitals, through calculated momentum profiles, provides some qualitative interpretation for the measured angular distributions of the TDCS.

Electron- and photon-impact ionization of furfural.

The He(i) photoelectron spectrum of furfural has been investigated, with its vibrational structure assigned for the first time. The ground and excited ionized states are assigned through ab initio calculations performed at the outer-valence Green's function level. Triple differential cross sections (TDCSs) for electron-impact ionization of the unresolved combination of the 4a″ + 21a' highest and next-highest occupied molecular orbitals have also been obtained. Experimental TDCSs are recorded in a combination of asymmetric coplanar and doubly symmetric coplanar kinematics. The experimental TDCSs are compared to theoretical calculations, obtained within a molecular 3-body distorted wave framework that employed either an orientation average or proper TDCS average. The proper average calculations suggest that they may resolve some of the discrepancies regarding the angular distributions of the TDCS, when compared to calculations employing the orbital average.

Dynamical (e,2e) studies of tetrahydropyran and 1,4-dioxane.

We present experimental and theoretical results for the electron-impact ionization of the highest occupied molecular orbitals of tetrahydropyran and 1,4-dioxane. Using an (e,2e) technique in asymmetric coplanar kinematics, angular distributions of the slow ejected electron, with an energy of 20 eV, are measured when incident electrons at 250 eV ionize the target and scatter through an angle of either -10° or -15°. The data are compared with calculations performed at the molecular 3-body distorted wave level. Fair agreement between the theoretical model and the experimental measurements was observed. The similar structures for these targets provide key insights for assessing the limitations of the theoretical calculations. This study in turn facilitates an improved understanding of the dynamics in the ionization process.

Triply differential (e,2e) studies of phenol.

We have measured (e,2e) triple differential cross sections (TDCS) for the electron-impact ionisation of phenol with coplanar asymmetrical kinematics for an incident electron energy of 250 eV. Experimental measurements of the angular distribution of the slow outgoing electrons at 20 eV are obtained when the incident electron scatters through angles of -5°, -10°, and -15°, respectively. The TDCS data are compared with calculations performed within the molecular 3-body distorted wave model. In this case, a mixed level of agreement, that was dependent on the kinematical condition being probed, was observed between the theoretical and experimental results in the binary peak region. The experimental intensity of the recoil features under all kinematical conditions was relatively small, but was still largely underestimated by the theoretical calculations.

A dynamical (e,2e) investigation of the structurally related cyclic ethers tetrahydrofuran, tetrahydropyran, and 1,4-dioxane.

Triple differential cross section measurements for the electron-impact ionization of the highest occupied molecular orbitals of tetrahydropyran and 1,4-dioxane are presented. For each molecule, experimental measurements were performed using the (e,2e) technique in asymmetric coplanar kinematics with an incident electron energy of 250 eV and an ejected electron energy of 20 eV. With the scattered electrons being detected at -5°, the angular distributions of the ejected electrons in the binary and recoil regions were observed. These measurements are compared with calculations performed within the molecular 3-body distorted wave model. Here, reasonable agreement was observed between the theoretical model and the experimental measurements. These measurements are compared with results from a recent study on tetrahydrofuran [D. B. Jones, J. D. Builth-Williams, S. M. Bellm, L. Chiari, C. G. Ning, H. Chaluvadi, B. Lohmann, O. Ingolfsson, D. Madison, and M. J. Brunger, Chem. Phys. Lett. 572, 32 (2013)] in order to evaluate the influence of structure on the dynamics of the ionization process across this series of cyclic ethers.

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 7b(2) and 10a(1) 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.

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.

Low energy (e, 2e) study from the 1t(2) orbital of CH4.

Single ionization of the methane (CH(4)) 1t(2) orbital by 54 eV electron impact has been studied experimentally and theoretically. The measured triple differential cross sections cover nearly a 4π solid angle for the emission of low energy electrons and a range of projectile scattering angles. Experimental data are compared with theoretical calculations from the distorted wave Born approximation and the molecular three-body distorted wave models. It is found that theory can give a proper description of the main features of experimental cross section only at smaller scattering angles. For larger scattering angles, significant discrepancies between experiment and theory are observed. The importance of the strength of nuclear scattering from the H-nuclei was theoretically tested by reducing the distance between the carbon nuclei and the hydrogen nuclei and improved agreement with experiment was found for both the scattering plane and the perpendicular plane.

Manipulating atomic fragmentation processes by controlling the projectile coherence.

We have measured the scattering angle dependence of cross sections for ionization in p+H2 collisions for a fixed projectile energy loss. Depending on the projectile coherence, interference due to indistinguishable diffraction of the projectile from the two atomic centers was either present or absent in the data. This shows that, due to the fundamentals of quantum mechanics, the preparation of the beam must be included in theoretical calculations. The results have far-reaching implications on formal atomic scattering theory because this critical aspect has been overlooked for several decades.

Low energy (e,2e) studies from CH4: results from symmetric coplanar experiments and molecular three-body distorted wave theory.

Low energy experimental and theoretical triply differential cross sections are presented for electron impact ionization of methane (CH(4)) for both the highest occupied molecular orbital (HOMO) and next highest occupied molecular orbital (NHOMO). The HOMO is a predominantly p-type orbital which is labeled 1t(2) and the NHOMO is predominantly s-type labeled 2a(1). Coplanar symmetric (symmetric both in final state electron energies and observation angles) are presented for final state electron energies ranging from 2.5 to 20 eV. The theoretical M3DW (molecular three-body distorted wave) results are in surprisingly good agreement with experiment for the HOMO state and less satisfactory agreement for the NHOMO state. The molecular NHOMO results are also compared with the ionization of the 2s shell of neon which is the isoelectronic atom.

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.

Differential cross sections for the ionization of oriented H2 molecules by electron impact.

A nonperturbative close-coupling technique is used to calculate differential cross sections for the electron-impact ionization of H2 at an energy of 35.4 eV. Our approach allows cross sections for any orientation of the molecule with respect to the incident electron beam to be analyzed. New features in the resulting cross sections are found compared with the case where the molecular orientation is averaged, and also with cross sections for He at equivalent electron kinematics. When averaged over all possible molecular orientations, good agreement is found with recent experimental results.

Experimental and theoretical (e,2e) ionization cross sections for a hydrogen target at 75.3 eV incident energy in a coplanar asymmetric geometry.

Very recently it was shown that the molecular three-body distorted wave (M3DW) approach gives good agreement with the shape of the experimental data for electron-impact ionization of H(2) in a coplanar symmetric geometry, providing the incident electrons have an energy of 35 eV or greater. One of the weaknesses of these studies was that only the shape of the cross section could be compared to experiment, since there was no absolute or relative normalization of the data. Here we report a joint experimental/theoretical study of electron-impact ionization of H(2) in a coplanar asymmetric geometry where the energy of the incident electron was fixed, and different pairs of final state electron energies were used. In this case, the experimental data can be normalized such that only one renormalization factor is required. It is shown that the M3DW is pretty good in agreement with experiment. However, a better treatment of polarization and exchange between the continuum and bound state electrons is required before quantitative agreement between experiment and theory is achieved.

Unexpected higher-order effects in charged particle impact ionization at high energies.

Most of the experimental and theoretical studies of electron-impact ionization of atoms, referred to as (e, 2e), have concentrated on the scattering plane. The assumption has been that all the important physical effects will be observable in the scattering plane. However, very recently it has been shown that, for C6+-helium ionization, experiment and theory are in nice agreement in the scattering plane and in very bad agreement out of the scattering plane. This lack of agreement between experiment and theory has been explained in terms of higher-order scattering effects between the projectile and target ion. We have examined electron-impact ionization of magnesium and have observed similar higher-order effects. The results of the electron-impact ionization of magnesium indicate the possible deficiencies in the calculation of fully differential cross sections in previous heavy particle ionization work.

Young-type interference in (e, 2e) ionization of H(2).

We have investigated the electron impact single ionization of the hydrogen molecule, with fully determined kinematics. The experimental and theoretical results are compared with He ionization under the same conditions. The results indicate that the ejected electron angular distribution for H(2) is modified due to Young-type interference between ionization amplitudes for scattering from the two centers in the hydrogen molecule. The observable result is a suppression of the backward scattering (recoil) peak compared with the binary peak.

An elementary method for calculating orientation-averaged fully differential electron-impact ionization cross sections for molecules.

Currently there are no reliable theoretical approaches for calculating fully differential cross sections (FDCS) for low-energy electron-impact ionization of large molecules. We have recently introduced the distorted-wave impulse approximation as a first step in developing improved theoretical approaches. One significant obstacle to evaluating improved theoretical approaches which require significant computer resources lies in the fact that the existing experimental data require taking averages over all molecular orientations. To circumvent this problem, it has been proposed to approximate the orientation-average by using an orientation-averaged molecular orbital in the calculation of the FDCS. The theoretical justification and expected range of validity for the approximation is given in this paper. Examples are presented for electron-impact ionization of H(2) and N(2).

Distorted wave Born and three-body distorted wave Born approximation calculations of the fully differential cross section for electron-impact ionization of nitrogen molecules.

Currently there are no reliable theoretical approaches for calculating fully differential cross sections (FDCSs) for low-energy electron-impact ionization of large molecules. We have recently proposed the orientation-averaged molecular orbital (OAMO) for calculating cross sections averaged over molecular orientations. In this paper, we use the OAMO to calculate distorted wave Born approximation (DWBA) and molecular three-body distorted wave (M3DW) Born approximation FDCS for electron-impact ionization of the nitrogen molecule. Both coplanar symmetric and asymmetric FDCSs are investigated in the energy range of 35.6-400 eV. By comparing with the experimental data, we found that the M3DW is reasonably accurate in this energy range. We also found that the postcollision interaction plays a sufficiently important role and that the DWBA is not reliable.

Role of the ground state in electron-atom double ionization.

Recently, absolute measurements have been reported for double ionization of helium by 5.6 keV electron-impact. At this high energy, one would think that the first Born approximation for the interaction of the projectile with the atom would be valid. However, on the basis of a lowest-order implementation of a Faddeev-type approach, Berakdar [Phys. Rev. Lett. 85, 4036 (2000)]] concluded that the approximation was not valid. Here we argue that (i) it is valid at this energy and (ii) the previous discrepancy between calculations in the first Born approximation and the overall magnitude of the measurements was due to a poor description of the ground state.