| Abstract: |
| The conformers of allyl alcohol and allyl mercaptan were studied with B3LYP/aug-cc-pVTZ method. Their relative energies were calculated at MP3, MP4(SDQ), and CCSD(T) levels. The most stable conformers for these two molecules are Gauche-gauche' (Gg'). The theo-retical photoelectron spectra simulated with the calculated ionization energies demonstrate that there are at least four conformers in allyl alcohol and four conformers in allyl mercaptan in the gas-phase experiments. The Dyson orbitals of the highest occupied molecular orbital (HOMO) and the next HOMO (HOMO-1) of allyl mercaptan Gg' conformer show strongly mixing nS and πC=C characteristics, which may be due to the resonance and inductive effects between πC=C and nS in HOMO-1 and HOMO. |
| Key words: Ab initio calculation, Ionization energy, Photoelectron spectroscopy, Dyson orbital |
| FundProject: |
附件 |
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| 烯丙醇和烯丙硫醇构象的Dyson轨道和电离能 |
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杨聚宝, 王美婷, 王克栋*, 刘玉芳
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河南师范大学物理与电子工程学院，新乡453007
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| 摘要: |
| 用B3LYP/aug-cc-pVTZ方法研究了烯丙醇和烯丙硫醇的构象. 采用MP3、MP4(SDQ)和CCSD(T)方法计算了它们的相对能量，这两种分子Gg0构象均最稳定. 根据理论计算的电离能模拟的光电子能谱说明在气相实验中烯丙醇和烯丙硫醇至少存在四种构象. 烯丙硫醇最外壳层和次外壳层的Dyson轨道均显示出强烈的nS和πC=C混合特征，这是由于S的孤对电子轨道和C=Cπ轨道之间的共振效应和诱导效应引起的. |
| 关键词: 从头算，电离能，光电子能谱，Dyson轨道 |
| DOI：10.1063/1674-0068/26/04/381-386 |
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