Quantum dynamics studies of chemical reactions

化学反应的量子动力学研究

• 批准号: 12440162
• 负责人: KATO Shigeki
• 金额: $ 8.45万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440162/
• 关键词: chemical reaction; potential energy surfaces; quantum dynamics; photo-dissociation; 振動励起状態; レベル統計

We carried out ab initio electronic structure and quantum dynamics calculations for the dissociative attachment process of electron to H_3^+, unimolecular reactions of H_2CO, and photo-dissociation dynamics of NOCI in the UV region. We developed an effective Hamiltonian for describing the quantum dynamics of H_3 Rydberg states and the relaxation dynamics of highly excited Rydberg Etatesleading to the dissociation channel swasexamined.A global potential energy function of H_2CO, which can describe both the molecular dissociative and isomerization channels, was constructed and the cumulative reaction probabilities of these channels were calculated with using the Watson Hamiltonian. An efficient algorithm was devised to treat the vibrational angular momentum term. For NOCI, analytical potential functions for seven states were constructed based on MRCI calculations and the quantum dynamics calculations were carried out to obtain the electronic and Raman spectral profiles as well as a full list of vibrational states on the ground state surface. We also examined the photo-dissociation dynamics at A band region and explain many experimental findings in a consistent way.

我们对电子与H_3^+的解离附着过程、H_2CO的单分子反应以及NOCI在紫外区的光解离动力学进行了从头算的电子结构和量子动力学计算。我们开发了一种有效的哈密顿量来描述H_3里德堡态的量子动力学和导致解离通道的高激发里德堡态的弛豫动力学。构建了H_2CO的全局势能函数，它可以描述分子解离通道和异构化通道并使用 Watson Hamiltonian 计算这些通道的累积反应概率。设计了一种有效的算法来处理振动角动量项。对于NOCI，基于MRCI计算构建了七种状态的分析势函数，并进行了量子动力学计算以获得电子和拉曼光谱分布以及基态表面振动状态的完整列表。我们还检查了 A 带区域的光解离动力学，并以一致的方式解释了许多实验结果。

项目成果

H.Nakamura: "State Resolved Reaction Rates of the Spin-forbidden Predissociation of N2O : A Quantum Dynamic Study of the Rotational Effect"Journal of Chemical Physics. 112. 1785-1796 (2000)

H.Nakamura：“N2O 自旋禁阻预解离的状态解析反应速率：旋转效应的量子动力学研究”化学物理杂志。

T.Yamamoto: "Full-dimensional Quantum Dynamics Study on the Mode-specific Unimolecular Dissociation Reaction of HFCO"Journal of Chemical Physics. 112. 8006-8016 (2000)

T.Yamamoto：“HFCO 模式特定单分子解离反应的全维量子动力学研究”化学物理杂志。

S.Iuchi: "Molecular dynamics simulation with the charge response kernel : Vibrational spectra of liquid water and N-methylacetoamide in aqueous solution"Journal of Physical Chemistry B. 106. 3466-3476 (2002)

S.Iuchi：“使用电荷响应核的分子动力学模拟：水溶液中液态水和 N-甲基乙酰胺的振动光谱”物理化学杂志 B. 106. 3466-3476 (2002)

Excited-state electronic structures and dynamics of NOCI : A new potential function set, absorption spectrum, and photodissociation mechanism

NOCI 的激发态电子结构和动力学：新的势函数集、吸收光谱和光解离机制

• 期刊: J.Chem.Phys. (in press)
• 作者: T.Yonehara;T.Yamamoto S.Kato;T.Yamashita S.Kato
• 通讯作者: T.Yamashita S.Kato

Cumulative reaction probabilities for the unimolecular dissociation and isomerization reactions of formaldehyde

甲醛单分子解离和异构化反应的累积反应概率

• 发表时间: 2004
• 期刊: Chem.Phys.Lett. 393
• 作者: T.Yonehara;T.Yamamoto;S.Kato
• 通讯作者: S.Kato