A Missing Puzzle in Dissociative Electron Attachment to Biomolecules: The Detection of Radicals

Ionizing radiation releases a flood of low-energy electrons that often causes the fragmentation of the molecular species it encounters. Special attention has been paid to the electrons’ contribution to DNA damage via the dissociative electron attachment (DEA) process. Although numerous research groups worldwide have probed these processes in the past, and many significant achievements have been made, some technical challenges have hindered researchers from obtaining a complete picture of DEA. Therefore, this research perspective calls urgently for the implementation of advanced techniques to identify non-charged radicals that form from such a decomposition of gas-phase molecules. Having well-described DEA products offers a promise to benefit society by straddling the boundary between physics, chemistry, and biology, and it brings the tools of atomic and molecular physics to bear on relevant issues of radiation research and medicine.

Regularized machine learning on molecular graph model explains systematic error in DFT enthalpies

A major goal of materials research is the discovery of novel and efficient heterogeneous catalysts for various chemical processes. In such studies, the candidate catalyst material is modeled using tens to thousands of chemical species and elementary reactions. Density Functional Theory (DFT) is widely used to calculate the thermochemistry of these species which might be surface species or gas-phase molecules. The use of an approximate exchange correlation functional in the DFT framework introduces an important source of error in such models. This is especially true in the calculation of gas phase molecules whose thermochemistry is calculated using the same planewave basis set as the rest of the surface mechanism. Unfortunately, the nature and magnitude of these errors is unknown for most practical molecules. Here, we investigate the error in the enthalpy of formation for 1676 gaseous species using two different DFT levels of theory and the ‘ground truth values’ obtained from the NIST database. We featurize molecules using graph theory. We use a regularized algorithm to discover a sparse model of the error and identify important molecular fragments that drive this error. The model is robust to rigorous statistical tests and is used to correct DFT thermochemistry, achieving more than an order of magnitude improvement.

Na-Influenced Bulk and Surface Properties of the So-Called Iota(ι)-Alumina: Spectroscopy and Microscopy Studies

The test alumina (the so-called ι-Al2O3) was thermally recovered at 1,100°C from chitosan-AlOx hybrid films and found to contain Na and Ca impurity ions inherited from the parent chitosan. Two different modifications of pure alumina, namely, γ- and α-Al2O3, were adopted as control samples. The test and control aluminas were examined for 1) the bulk elemental constitution by atomic absorption spectroscopy (AAS), 2) the surface chemical composition by X-ray photoelectron spectroscopy (XPS), 3) the bulk phase composition by X-ray powder diffractometry (XRD), ex-situ Fourier-transform infrared spectroscopy (IR), and Laser Raman (LRa) spectroscopy, 4) the surface area, topography, and morphology by N2 sorptiometry, and atomic force (AFM) and scanning electron microscopy (SEM), 5) the surface adsorptive interactions with pyridine and 2-propanol gas-phase molecules by in-situ IR spectroscopy of the adsorbed species, and 6) the surface catalytic interactions with 2-propanol gas-phase molecules by in-situ IR spectroscopy of the gas phase. Results obtained could clearly show that the test alumina (ι-Al2O3) is only hypothetically pure alumina since in reality its bulk structure is majored by mullite-type Na-aluminate (Na0.67Al6O9.33/NaAlO2) and minored by Na-β-alumina (Na1.71Al11O17) and β-alumina (NaAl11O17). Consistently, observed Na-influenced modifications of the surface chemistry, topology, and morphology, as well as adsorptive and catalytic interactions with pyridine and 2-propanol gas-phase molecules, showed significant deviations from those exhibited by the control pure aluminas (γ- and α-Al2O3).

Computational UV Spectra for Amorphous Solids of Small Molecules

Ices in the interstellar medium largely exist as amorphous solids composed of small molecules including ammonia, water, and carbon dioxide. Describing gas-phase molecules can be readily accomplished with current high-level...

Selecting two-photon sequential ionization pathways in H2 through harmonic filtering

Recent experiments in gas-phase molecules have shown the versatility of using attosecond pulse trains combined with IR femtosecond pulses to track and control excitation and ionization yields on the attosecond...

Computational approaches to dissociative chemisorption on metals: Towards chemical accuracy

We review the state-of-the-art in the theory of dissociative chemisorption (DC) of small gas phase molecules on metal surfaces, which is important to modeling heterogeneous catalysis for practical reasons, and...