首页|2-甲基烯丙醇的结构和振动光谱研究

2-甲基烯丙醇的结构和振动光谱研究

扫码查看
原文链接
  • NETL
  • NSTL
  • 万方数据
近几十年来,分子内O-H…π氢键引起了广泛的研究兴趣.本文利用红外-真空紫外非共振电离检测红外光谱方法研究了中性和阳离子态的2-甲基烯丙醇的分子结构.密度泛函理论计算揭示了五个稳定的中性2-甲基烯丙醇构象和三个稳定的阳离子2-甲基烯丙醇构象.根据OH基团指向C=C双键的结构特征,两个中性2-甲基烯丙醇构象具有O-H…π分子内氢键相互作用.本文测量了中性(2700～3700 cm-1)和阳离子2-甲基烯丙醇(2500～7200 cm-1)的红外光谱,并在B3LYP-D3(BJ)/def2-TZVPP水平上计算了非谐振动红外光谱.观察到中性2-甲基烯丙醇的OH伸缩振动在3656 cm-1处,略低于甲醇和乙醇.相比之下,阳离子2-甲基烯丙醇的OH伸缩振动与中性2-甲基烯丙醇相比红移约140 cm-1.相互作用区域指示函数和自然键轨道分析表明,中性2-甲基烯丙醇中的O-H…π相互作用较弱,在稳定中性2-甲基烯丙醇中不起主要作用.
Structure and Vibrational Spectroscopy of 2-Methylallyl Alcohol
The intramolecular O-H…π hydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)non-resonant ionization detected IR spec-troscopy(NRID-IR)method to study the molecular structure of neutral and cationic 2-methylallyl alcohol(MAA,CH2=C(CH3)-CH2-OH).Density functional theory calcu-lations revealed five stable neutral and three stable cationic MAA conformers,respective-ly.Two neutral MAA conformers are expect-ed to have an O-H…π intramolecular hy-drogen bond interaction,based on the struc-tural characterization that the OH group is directed toward the C=C double bond.The IR spectra of both neutral(2700-3700 cm-1)and cationic MAA(2500-7200 cm-1)were mea-sured,and the anharmonic IR spectra were calculated at the B3LYP-D3(BJ)/def2-TZVPP level.The OH stretching vibration frequency of neutral MAA was observed at 3656 cm-1,slightly lower than those of methanol and ethanol.In contrast,the OH stretching vibration of cationic MAA was red-shifted by about 140 cm-1 compared to neutral MAA.The interaction region indicator and natural bond orbital analysis suggest that the O-H…π interaction in neutral MAA is weak,and may not play a major role in stabilizing the neutral MAA.

Gas phase infrared spectroscopyMolecular structureIntramolecular hydrogen bondNatural bond orbital analysis

肖彭飞、刘思越、周小虎、黄恩德、仲立成、张未卿、樊红军、杨学明、董文锐

展开 >

中国科学技术大学化学物理系,合肥 230026

中国科学院大连化学物理研究所分子反应动力学国家重点实验室,大连 116023

大连理工大学物理学院,三束材料改性教育部重点实验室,大连 116024

中国科学院大学,北京 100049

沈阳化工大学化学工程学院,沈阳 110142

南方科技大学化学系,深圳 518055

合肥国家实验室,合肥 230088

展开 >

气相红外光谱 分子结构 分子内氢键 自然键轨道分析

Dalian Coherent Light Source(DCLS)National Natural science Foundation of ChinaChinese Academy of SciencesInnovation Program for Quantum Science and Technology

22288201GJJSTD202200012021ZD0303305

2024

10.1063/1674-0068/cjcp2309078

化学物理学报(英文版)
中国物理学会

化学物理学报(英文版)

CSTPCDEI
影响因子：0.162
ISSN：1674-0068
年,卷(期)：2024.37(4)