Self-association of oxime: electronic and vibrational structures of formaldoxime monomer, dimer, and trimer

Abstract

The self-association of oxime is investigated from the aspect of intermolecular hydrogen bonding through ab initio SCF MO calculations on formaldoxime monomer, dimer, and trimer. It is understood from population analysis that formaldoxime monomer has inherently a suitable electronic distribution for constructing OH⋯3N hydrogen-bonded cyclic dimer and trimer. The formaldoxime trimer is characterized as the depressed nine membered ring. It is also confirmed to be more stable and preferable as a predominantly existing species than the dimer, which accounts for the experimental value of average association number for oximes. Vibrational analysis reveals that upon the self-association the OH stretching vibration is red-shifted, while both the OH in-plane and out-of-plane bending ones are blue-shifted, the results of which lead to a global feature of motion that ring wagging and ring puckering are activated. Largely enhanced intensities of IR-active OH stretching vibrations are well rationalized with more prominent charge polarization centered around =NOH sites in the formaldoxime dimer and trimer.