丙烯酰基正离子的红外光解离光谱研究  

Infrared photodissociation spectroscopic and theoretical study of the H_3C_3O^+ and D_3C_3O^+ acryloyl cations

作　　者：李巍 金佳晔 王冠军 周鸣飞 Wei Li, Jiaye Jin, Guanjun Wang, Mingfei Zhou(Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials Department of Chemistry, Fudan University, Shanghai 200433, Chin)

机构地区：[1]复旦大学化学系上海市分子催化和功能材料重点实验室能源材料化学协同创新中心,上海200433

出　　处：《中国科学：化学》2018年第2期218-224,共7页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21433005;21688102)资助项目

摘　　要：利用脉冲激光溅射-超声分子束载带离子源在气相中产生了[H_3C_3O]^+和[D_3C_3O]^+离子及贴附CO的[H_3C_3O?CO]^+和[D_3C_3O?CO]^+络合物离子.通过贴附CO的络合物离子的红外光解离光谱实验获得了[H_3C_3O]^+和[D_3C_3O]^+离子的红外光谱.通过比较实验光谱和理论模拟光谱,确定了[H_3C_3O]^+离子为丙烯酰基正离子,其电子基态为~1A′,具有C_s对称性.适应性自然密度划分分析方法(Ad NDP)成键分析表明,丙烯酰基正离子除了定域的CH,CC,COσ键和两个简并COπ键以外,还存在一个离域的三中心两电子CCCπ键.The carbocations,H3C3O~＋and D3C3O~＋are produced via pulsed laser vaporization of a graphite target in supersonic expansions of helium seeded with carbon monoxide and acetylene or methane.The infrared spectra are measured via mass-selected infrared photodissociation spectroscopy of their CO-tagged[H3C3O？CO]~＋and[D3C3O？CO]~＋cation complexes.The geometry of the cation complex is determined by the infrared spectra in conjunction with theoretical calculations.The H3C3O~＋and D3C3O~＋core cations are determined to be acryloyl cations with^1A′electronic ground state and Cssymmetry.The Ad NDP bonding analysis indicates that besides the localized two-center-twoelectron（2c-2e）C–O,C–C,and C–Hσbonds as well as 2c-2e COπbonds,there is a delocalized three-center-twoelectron（3c-2e）CCCπbond.

关 键 词：丙烯酰基正离子 红外光解离光谱 理论计算 成键分析 

分 类 号：O621.13[理学—有机化学]