• chiral discrimination;
  • homo/heterochiral complexes;
  • polarized continuum model (PCM)


For the first time, the discrimination of different chiral forms of 1:1 complexes with hydrogen peroxide and methyl hydroperoxide have been investigated using density functional theory (DFT) and Møller–Plesset type 2 (MP2) methods at varied basis set levels from 6-31+G(d,p) to 6-31++G(2d,2p). Three pairs of chiral enantiomers were considered. The optimized geometric parameters, interaction energies, and chirodiastatic energies for various isomers at different levels are estimated. To take into account the water solvation effect, the polarized continuum model (PCM) method has been used to evaluate the ΔGsolv. The gas phase results show that the heterochiral six-membered ring complex (structure I) and homochiral five-membered ring complexes (structures IV and V) are preferred configurations for the three pairs of chiral enantiomers. The solvation effect on six-membered ring complexes (structures I and II) shows nonsignificant changes in the configurations preferred, but on five-membered ring complexes, the homo-/heterochiral preference is found to be inverse in the polar solvent. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006