低能量电子辐照液体甲醇产生负离子团簇

Anionic Clusters Produced in Low-Energy Electron Irradiation of Methanol Liquid

本文利用线形飞行时间质谱,在低能量电子与液体甲醇碰撞中探测到了负离子产物.利用量子化学计算,进一步确定负离子产物为氢键结合的分子团簇CH_(3)OH.CH_(3)O^(-)和CH_(3)OH.CH_(3)OH.CH_(3)O^(-),而且其单占据分子轨道表现为价层轨道特征.虽然CH_(3)OH.CH_(3)OH^(-)和CH_(3)OH.CH_(3)OH.CH_(3)OH^(-)对应各自势能面的极小点,但能量上相比脱氢团簇不具有产生优势,且其单占据分子轨道具有显著的溶剂化电子特征.

In the low-energy electron impacts with a liquid beam of methanol,we detect the anionic yields using a linear time-of-flight mass spectrometer.With help of quantum chemistry calculations,we further identify these anionic products as the hydrogenbondingclusters,i.e.,CHgOH·CHgO^(-)and CHgOH·CH:OH·CH_(3)O^(-),and their singly occupied molecular orbitals show the valence-bound feature.In contrast,CH_(3)OH^(-)CH_(3)OH and CH_(3)OH^(-)CH_(3)OH·CH_(3)OH are unfavored in energetics with respect to the dehydrogenated ones,although they also correspond to the minima on the potential energy surfaces.Furthermore,the singly occupied molecular orbitals of CH_(3)OH·CH_(3)OH and CH_(3)OH·CH_(3)OH·CH_(3)OH^(-)indicate the typical feature of aqueous-solvated electron.