The intramolecular O−H…πhydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)nonresonant ionization detected IR spectroscopy(NRI...The intramolecular O−H…πhydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)nonresonant ionization detected IR spectroscopy(NRID-IR)method to study the molecular structure of neutral and cationic 2-methylallyl alcohol(MAA,CH_(2)=C(CH_(3))−CH_(2)−OH).Density functional theory calculations revealed five stable neutral and three stable cationic MAA conformers,respectively.Two neutral MAA conformers are expected to have an O−H…πintramolecular hydrogen bond interaction,based on the structural 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 measured,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…πinteraction in neutral MAA is weak,and may not play a major role in stabilizing the neutral MAA.展开更多
基金The experimental work is supported by the National Natural Science Foundation of China(No.22241304,No.22225303)the National Natural Science Foundation of China(NSFC Center for Chemical Dynamics,No.22288201)+3 种基金the Scientific Instrument Developing Project of the Chinese Academy of Sciences(No.GJJSTD20220001)the Innovation Program for Quantum Science and Technology(No.2021ZD0303304)Xueming Yang also thanks the Guangdong Science and Technology Program(No.2019ZT08L455 and No.2019JC01X091)the Shenzhen Science and Technology Program(No.ZDSYS20200421111001787).
基金supported by the National Natural Sci-ence Foundation of China(No.21973092 and No.21873004)the National Key Research and Develop-ment Program of China(No.2018YFA0208703)+1 种基金Chinese Academy of Sciences(YSBR-007)Dalian In-stitute of Chemical Physics(DICP I202205).
基金supported by the National Natural Science Foundation of China(No.22125302,No.22173099,No.22288201,No.21873089,and No.21973037)the Guangdong Science and Technology Program(No.2019ZT08L455 and No.2019JC01X091)the Shenzhen Science and Technology Program(No.ZDSYS20200421111001787).
基金gratefully acknowledge the Dalian Coherent Light Source(DCLS)for support and assistanceThis work was supported by the National Natural Science Foundation of China(No.22288201)+1 种基金the Chinese Academy of Sciences(GJJSTD20220001)the Innovation Program for Quantum Science and Technology(No.2021ZD0303305).
文摘The intramolecular O−H…πhydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)nonresonant ionization detected IR spectroscopy(NRID-IR)method to study the molecular structure of neutral and cationic 2-methylallyl alcohol(MAA,CH_(2)=C(CH_(3))−CH_(2)−OH).Density functional theory calculations revealed five stable neutral and three stable cationic MAA conformers,respectively.Two neutral MAA conformers are expected to have an O−H…πintramolecular hydrogen bond interaction,based on the structural 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 measured,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…πinteraction in neutral MAA is weak,and may not play a major role in stabilizing the neutral MAA.
基金supported by the National Key Research and Development Program of(No.2021YFA1500601 and No.2018YFA0208703)the National Natural Science Foundation of China(No.21973010 and No.21973092)+3 种基金the Instrument Developing Project of the Chinese Academy of Sciences(No.YZ201504)the CAS Projects for Young Scientists in Basic Research(No.YSBR-007)the Dalian Institute of Chemical Physics Innovation Foundation(DICP I202205)LiaoNing Revitalization Talents Program(No.XLYC1907032).
