Fundamental processes of tunneling reaction

隧道反应的基本过程

• 批准号: 08240105
• 负责人: MIYAZAKI Tetsuo
• 金额: $ 44.67万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-08240105/
• 关键词: Tunneling reaction; Solid hydrogen; Tunneling displacement; Quantum effects; Nonadiabatic transition; Chemical reaction dynamics; Tritium; Reaction in cells; トンネル反応; 固体水素; 非断熱遷移; 核スピン一回転状態結合; 原子バブル; 銀ニ量体カチオン; ファンデルワールス錯体; ビタミンC; 量子拡散; ESR

The detailed mechanism of a tunneling reaction has not been studied previously. Here the several factors that control a tunneling reaction have been elucidated at ultralow temperature. The selective reaction caused by tunneling is presented in solid hydrocarbon. It is also shown that a tunneling reaction of vitamin C and long-1ived radicals in γ-irradiated cells is related to suppression of cancer.The temperature dependent ESR spectra of partially deuteriated cyclohexane radical cations were successfully analyzed in terms of dynamical averaging due to a tunneling displacement among the Jahn-Teller distorted C2h structures with different zero-point vibration energies. Furthermore, quantum effects of nuclear spin-rotation coupling were demonstrated for selectively deuteriated methyl radicals in low temperature argon matrix.Hydrogen atom transfer chemical reactions have been successfully conceptualized as vibrationally nonadiabatic transitions in the vicinity of potential ridge. New control scheme of molecular processes by time-dependent external fields has been proposed.Tunneling abstraction reaction of tritium(T), which is the heaviest hydrogen isotope, with isotopic hydrogen molecules was observed for the first time. It was proposed that the recombination of T and H proceeds through their bubble states in the liquid helium, which is the typical quantum liquid.

隧道反应的详细机理以前没有被研究过，在超低温下控制隧道反应的几个因素已经被阐明。还表明了在固体烃中发生隧道反应。维生素 C 和 γ 辐照细胞中的长寿命自由基与抑制癌症有关。由于具有不同零点振动能量的 Jahn-Teller 扭曲 C2h 结构之间的隧道位移此外，还证明了低温氩基质中选择性氘代甲基自由基的核自旋旋转耦合的量子效应。氢原子转移化学反应已成功概念化。作为势脊附近的振动非绝热跃迁，提出了由时间相关的外部场控制分子过程的新方案。氚（T）的隧道提取反应，它是最重的氢同位素，首次观察到同位素氢分子，T和H的重组是通过液氦（典型的量子液体）中的气泡态进行的。

项目成果

T.Miyazaki et al.: "Tunneling reaction of long-lived radicals and vitamin C in γ-irradiated mammalian cells"Radiat. Phys. Chem. 49. 547-551 (1997)

T. Miyazaki 等：“γ-照射的哺乳动物细胞中长寿命自由基和维生素 C 的隧道反应”Radiat Chem. 49. 547-551 (1997)

V.I.Osherov: "Quantum Mechanically Exact Analytical Solutions of a Two-state Exponential Model" J.Chem.Phys.105. 2770-2779 (1996)

V.I.Osherov：“二态指数模型的量子力学精确分析解”J.Chem.Phys.105。

Y. Aratono et al.: "Tunneling abstraction reactions of tritium atoms with HD in superfluid ィイD13ィエD1He-ィイD14ィエD1He media at 1.3 K"J. Phys. Chem. A. 102. 1501-1506 (1998)

Y. Aratono 等人：“1.3 K 下超流体介质中氚原子的隧道提取反应”J Chem. A. 102. 1501-1506 (1998)

T. Miyazaki et al.: "Quantum tunneling of D(H) atoms and HィイD3-(/)2ィエD3 anions in solid hydrogen"J. Low Temp. Phys.. 111. 453-461 (1998)

T. Miyazaki 等人：“固体氢中 D(H) 原子和 D3 阴离子的量子隧道效应”J. Low Temp. 111. 453-461 (1998)

M.Shiotani et al.: "Asymmetrically distorted structure, selective bond length alternation and reactions of radical cations of silacyclohexanes"J.Phys. Chem. A. 101. 6983-6990 (1997)

M.Shiotani 等人：“硅杂环己烷的不对称扭曲结构、选择性键长交替和自由基阳离子反应”J.Phys。