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

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• 作者：Jing Yang ; Xu Shan ; Zhe Zhang ; Yaguo Tang ; Minfu Zhao ; XiangJun Chen
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：December 18, 2014
• 年：2014
• 卷：118
• 期：50
• 页码：11780-11786
• 全文大小：362K
• ISSN：1520-5215

文摘

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 (C_2v) completely fails to interpret the large 鈥渢urn-up鈥?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 (C_2v) and bent (C_s) 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.