A high-resolution infrared spectroscopic investigation of the halogen atom–HCN entrance channel complexes solvated in superfluid helium droplets

摘要: Rotationally resolved infrared spectra are reported for the X–HCN (X = Cl, Br, I) binary complexes solvated in helium nanodroplets. These results directly compared with those obtained previously corresponding X–HF [J. M. Merritt, J. Kupper and R. E. Miller, Phys. Chem. Phys., 2005, 7, 67]. For bromine iodine atoms complexed HCN, two linear structures observed assigned to 2Σ1/2 2Π3/2 ground electronic states of nitrogen hydrogen bound geometries, respectively. Experiments HCN + chlorine give rise only a single band which is attributed isomer. That isomer not stabilized rationalized terms lowering isomerization barrier by spin–orbit coupling. Theoretical calculations without coupling have also been performed our experimental results. The possibility stabilizing high-energy containing multiple radicals discussed, motivated preliminary spectroscopic evidence di-radical Br–HCCCN–Br complex. Spectra molecular halogen HCN–X2 presented.