Systematic Study on Hydrated Arginine: Clear Theoretical Evidence for the Canonical-to-Zwitterionic Structure...

Extensive ab initio investigations have been performed to characterize the stable conformers of hydrated arginine (Arg-H₂O). Many new low-energy canonical Arg-H₂O conformers were identified and they are more stable than previous results. The large energy differences (more than 5.00 kcal mol^-1) between the canonical and zwitterionic Arg-H₂O isomers calculated by the composite CBS-QB3 method confirmed the dominance of the zwitterions. The micro effects of corrections of the zero-point energy and the basis set superposition error on the stability of hydrated isomers were carefully examined for the first time. The infrared (IR) spectra were simulated at a recommended temperature and the notable spectral differences enable the unambiguous identification of the different hydrated forms. Further transition state calculations revealed that the canonical Arg-H₂O can be transformed to the zwitterions using the amino group as a bridge. Our study thus shows valuable insights into the hydration of large flexible molecules and provides solid theoretical evidence for the canonical-to-zwitterionic structure transition of hydrated arginine.