Quantum chemical study of the reaction paths and kinetics of acetaldehyde formation on a methanol-water ice model.

Acetaldehyde (CH3CHO) is ubiquitous in interstellar space and is important for astrochemistry as it can contribute to the formation of amino acids through reaction with nitrogen containing chemical species. Quantum chemical and reaction kinetics studies are reported for acetaldehyde formation from the chemical reaction of C(3P) with a methanol molecule adsorbed at the eighth position of a cubic water cluster. We present extensive quantum chemical calculations for total spin S = 1 and S = 0. The UωB97XD/6-311++G(2d,p) model chemistry is employed to optimize the structures, compute minimum energy paths and zero-point vibrational energies of all reaction steps. For the optimized structures, the calculated energies are refined by CCSD(T) single point computations. We identify four transition states on the triplet potential energy surface (PES), and one on the singlet PES. The reaction mechanism involves the intermediate formation of CH3OCH adsorbed on the ice cluster. The rate limiting step for forming acetaldehyde is the C-O bond breaking in CH3OCH to form adsorbed CH3 and HCO. We find two positions on the reaction path where spin crossing may be possible such that acetaldehyde can form in its singlet spin state. Using variational transition-state theory with multidimensional tunnelling we provide thermal rate constants for the energetically rate limiting step for both spin states and discuss two routes to acetaldehyde formation. As expected, quantum effects are important at low temperatures.

Bound Electron Enhanced Radiosensitisation of Nimorazole upon Charge Transfer.

This novel work reports nimorazole (NIMO) radiosensitizer reduction upon electron transfer in collisions with neutral potassium (K) atoms in the lab frame energy range of 10-400 eV. The negative ions formed in this energy range were time-of-flight mass analyzed and branching ratios were obtained. Assignment of different anions showed that more than 80% was due to the formation of the non-dissociated parent anion NIMO•- at 226 u and nitrogen dioxide anion NO2- at 46 u. The rich fragmentation pattern revealed that significant collision induced the decomposition of the 4-nitroimidazole ring, as well as other complex internal reactions within the temporary negative ion formed after electron transfer to neutral NIMO. Other fragment anions were only responsible for less than 20% of the total ion yield. Additional information on the electronic state spectroscopy of nimorazole was obtained by recording a K+ energy loss spectrum in the forward scattering direction (θ ≈ 0°), allowing us to determine the most accessible electronic states within the temporary negative ion. Quantum chemical calculations on the electronic structure of NIMO in the presence of a potassium atom were performed to help assign the most significant lowest unoccupied molecular orbitals participating in the collision process. Electron transfer was shown to be a relevant process for nimorazole radiosensitisation through efficient and prevalent non-dissociated parent anion formation.