Ring-Puckering Effects on Electron Momentum Distributions of Valence Orbitals of Oxetane

The binding energy spectra and electron momentum distributions for the outer-valence molecular orbitals of oxetane have been measured utilizing (e, 2e) electron momentum spectrometer with non-coplanar asymmetric geometry at the impact energy of 2500 eV. The experimental momentum distributions were compared with the density functional theory calculations employing B3LYP hybrid functional with aug-cc-pVTZ basis set. It was found that the calculation at planar geometry (C2v) completely fails to interpret the large “turn-up” at low momentum region in electron momentum distribution of the highest occupied molecular orbital (HOMO) 3b1, while the calculations considering the thermal abundances of planar (C2v) and bent (Cs) conformers or the thermally populated vibrational states of ring-puckering motion have significantly improved the agreement. The results indicate that the ring-puckering motion of oxetane has a strong effect on the electron density distribution of HOMO.