| Project/Area Number |
20550005
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Physical chemistry
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| Research Institution | Tohoku University |
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Principal Investigator |
MIKAMI Naohiko Tohoku University, 大学院・理学研究科, 名誉教授 (70004447)
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| Co-Investigator(Renkei-kenkyūsha) |
YOSHIYUKI Matsuda 東北大学, 大学院・理学研究科, 助教 (70400223)
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| Project Period (FY) |
2009 – 2010
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| Project Status |
Completed (Fiscal Year 2010)
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| Budget Amount *help |
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2010: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2009: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2008: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
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| Keywords | 分子分光 / 反応中間体構造解析 / 芳香族求核置換反応中間体 / σ-complex / 分子クラスター / ベンゼン・メタノールクラスター / プロトン付加水クラスター / アセトン2量体 / 光イオン化誘起異性化反応 / C_6F_6・NH_3クラスター / フォルムアミド・水クラスター / 水素結合形態変化 / 水和メタノールクラスター / HCP分子 / 前期解離反応機構 / レーザー分光 / 気相イオン / 反応制御 |
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| Research Abstract |
Spectroscopic studies on jet-cooled molecular cluster cations have been carried out for the following systems ;
1. IR and electronic spectroscopy of [C_6H_6(NH_3)_n]^+ (n=1 and 2) revealed that their stable forms are of s-complex type, in which the ammonia moiety is covalently bonded to the benzene moiety as expected as the reaction intermediate of nucleophilic substitution of aromatics. The similar structures of [Benzene-(Methanol)_n]^+ (n=2, 3) were also investigated in combination with quantum chemical calculations.
2. H-bond network structures of H^+(H_2O)_n (n=20-200) were investigated by IR spectroscopy. It was found that the spectral features of the clusters with increasing cluster size become similar to the characteristic features of water and of ice, indicating the network morphology of the large-size clusters transmutes gradually to those of the bulk systems. It was also found that the spectral feature depends on the internal energy in the species.
3.Structures of neutral and cationic clusters of acetone and of acetic acid were investigated by using IR spectroscopy based on vacuum-ultraviolet one-photon ionization detection. It was found that the keto-enol transition is generated after the ionization for many clusters, such as their dimers, whereas their neutrals are of the keto-form. The isomerization mechanism was discussed in relation to their proton affinities and the potential surface of the proton-transfer coordinate.
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