Lanczos-based equation-of-motion coupled-cluster singles-and-doubles approach to the total photoionization cross section of valence excited states

We report on a combination of experimental and theoretical investigations into the structure of electronically excited para-benzoquinone (pBQ). Here synchrotron photoabsorption measurements are reported over the 4.0-10.8 eV range. The higher resolution obtained reveals previously unresolved pBQ spectral features. Time-dependent density functional theory calculations are used to interpret the spectrum and resolve discrepancies relating to the interpretation of the Rydberg progressions. Electron-impact energy loss experiments are also reported. These are combined with elastic electron scattering cross section calculations performed within the framework of the independent atom modelscreening corrected additivity rule plus interference (IAM-SCAR + I) method to derive differential cross sections for electronic excitation of key spectral bands. A generalized oscillator strength analysis is also performed, with the obtained results demonstrating that a cohesive and reliable quantum chemical structure and cross section framework has been established. Within this context, we also discuss some issues associated with the development of a minimal orbital basis for the single configuration interaction strategy to be used for our high-level low-energy electron scattering calculations that will be carried out as a subsequent step in this joint experimental and theoretical investigation.

Superoxide anions colliding with benzene molecules at impact energies from 200 to 900 eV are reported for the first time to form massive complexes. With the aid of quantum chemistry calculations, we propose a mechanism in which a sudden double ionization of benzene and the subsequent electrostatic attraction between the dication and the anion form a stable covalently bonded C6H6O2+ molecule, that evolves towards the formation of benzene-diol conformers. These findings lend support to a model presenting a new high energy anion-driven chemistry as an alternative way to form complex molecules.

We report novel data on ion-pair formation in hyperthermal (30–800 eV) neutral potassium collisions with neutral pyrimidine (Pyr, C 4 H 4 N 2 ) molecules. In this collision regime, negative ions formed by electron transfer from the alkali atom to the target molecule were time-of-flight mass analyzed and the fragmentation patterns and branching ratios have been obtained. The most abundant product anions have been assigned to CN − and C 2 H − and the electron transfer mechanisms are comprehensively discussed. Particular importance is also given to the efficient loss of integrity of the pyrimidine ring in the presence of an extra electron, which is in contrast to dissociative electron attachment experiments yielding the dehydrogenated parent anion. Theoretical calculations were performed for pyrimidine in the presence of a potassium atom and provided a strong basis for the assignment of the lowest unoccupied molecular orbitals accessed in the collision process. In order to further our knowledge about the collision dynamics, potassium cation (K + ) energy loss spectrum has been obtained and within this context, we also discuss the role of the accessible electronic states. A vertical electron affinity of (−5.69 ± 0.20) eV was obtained and may be assigned to a ( b 1 ) state that leads to CN − formation.

This work demonstrates that selective excision of hydrogen atoms at a particular site of the DNA base adenine can be achieved in collisions with electronegative atoms by controlling the impact energy. The result is based on analysing the time-of-flight mass spectra yields of potassium collisions with a series of labeled adenine derivatives. The production of dehydrogenated parent anions is consistent with neutral H loss either from selective breaking of C-H or N-H bonds.

Experimental electron-detachment cross sections for collisions of Experimental electron-detachment cross sections for collisions of O2-with N2 Experimental electron-detachment cross sections for collisions of O2-with N2 molecules in the energy range 50-7000 eV molecules in the energy range 50-7000 eV

We have performed comprehensive charge-transfer experiments yielding negative ion formation in collisions of fast neutral potassium atoms with nitroimidazole and methylated derivative molecules. The anionic pattern reveals that in the unimolecular decomposition of the precursor parent anion, single and multiple bond cleavages are attained. Selective excision of hydrogen atoms from the N1 position in 4-nitroimidazole (4NI) is completely blocked upon methylation in 1-methyl-4-nitroimidazole (1m4NI) and 1-methyl-5-nitroimidazole (1m5NI). Additionally, only 4NI and 2-nitroimidazole (2NI) are efficient in selectively producing neutral •OH and NO• radicals in contrast to 1m4NI and 1m5NI. These findings present a novel experimental evidence of selective chemical bond breaking by just tuning the proper collision energy in atom–molecule collision experiments. The present work contributes to the current need of pinpointing a class of charge-transfer collisions that exhibit selective reactivity of the kind demonstrated here, extending to tailored chemical control for different applications such as tumor radiation therapy through nitroimidazole-based radiosensitization.

This work reports on the use of two different Monte Carlo codes (GEANT4 and MCNPX) for assessing the dose reduction using bismuth shields in computer tomography (CT) procedures in order to protect radiosensitive organs such as eye lens, thyroid and breast. Measurements were performed using head and body PMMA phantoms and an ionisation chamber placed in five different positions of the phantom. Simulations were performed to estimate Computed Tomography Dose Index values using GEANT4 and MCNPX. The relative differences between measurements and simulations were <10 %. The dose reduction arising from the use of bismuth shielding ranges from 2 to 45 %, depending on the position of the bismuth shield. The percentage of dose reduction was more significant for the area covered by the bismuth shielding (36 % for eye lens, 39 % for thyroid and 45 % for breast shields).