Radicals in ammonium tartrate at 295 K by X-radiation: Revised radical structures by EMR and DFT analyses

Abstract

The simple amino acid l-α-alanine (ala) in polycrystalline form was among the first substances to be proposed and subsequently developed for Electron Paramagnetic Resonance (EPR)-based solid state radiation dosimetry. One disadvantage with ala is a relatively low sensitivity for doses below a few gray (Gy) which is a dose range of particular interest in medical, accident and environmental applications. A number of other compounds have been screened and some of these have shown a better sensitivity to radiation exposure than ala, in some cases up to a factor of 7–8. In particular ammonium tartrate (AT) and lithium formate (LiFo) have been taken into practical use. The present work was initially aimed to investigate the low-temperature radical products in AT, and the reactions leading to the product of dosimetric interest at room temperature. As a part of these studies, the previously characterized major room temperature radical product was re-investigated using single crystal electron magnetic resonance (EMR) techniques combined with periodic density functional theory (DFT) -type quantum chemical calculations. Surprisingly, this study showed that the molecular structure of the dominant radical at room temperature is somewhat different from that previously proposed. Furthermore, a second room temperature radical, previously not well characterized, was carefully investigated and three hyperfine coupling tensors were determined. These three tensors were sufficient to simulate all experimental observations for the second radical but not alone sufficient to permit an unambiguous molecular structure of the defect to be determined. It appears that the EPR resonance from this radical does not influence the dosimetric potential of AT.