Theoretical Studies on the Dynamics of Clusters and Excited States

团簇和激发态动力学的理论研究

• 批准号: 01470016
• 负责人: NAKATSUJI Hiroshi
• 金额: $ 4.42万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470016/
• 关键词: van der Waals molecule; metal cluster; excited state; electronic spectra; collision induced absorption; chemisorption; metal surface; イオン化状態; アニオン状態; 量子化学理論; CsXe; SAC; SAC-CI理論; EGWF; EX-EGWF理論

Reactions and dynamics of van der Waals molecules and metal clusters are topics of recent experimental and theoretical studies. In this research project, we have studied several subjects of these topics by quantumchemical methods. Some of them are as follows.(1) Potential energy curves of the round, excited, and ionized states of the Ven der Waals molecules such as Ar_2, Kr_2, ArF, and CsRg (Rg=Ne, Ar, Kr, Xe) are studied by the SAC/SAC-CI method. For Ar_2, the results for the 4s, and 4p Rydberg stated compare very well with the experimental results of the absorption and emission spectra. Some new assignments of the observed spectra are given, particularly for the excitations from the bound excited states. For the CsRg system, the SAC-CI potential curves and the (induced) transition moments have reproduced well the observed collision induced absorption spectra. We could then clarify the detailed electronic processes included in the observed collision induced absorption spectra.(2) The … More Exponentially Generated Wave Function (EGWF) method is proposed as a generalization of the SAC method. The excitator method applied to the EGWF method is proposed as a generalization of the SAC-CI method. These methods are applied to the various ground, excited, ionized, and anion states of C_2, CO, HF, etc at normal and elongated distances with very good agreement with the full CI (exact) solutions. The result implies that we have prepared the theory for the ground, excited, ionized, and anion states which is applicable for any states with arbitrary nuclear configurations. The method has also been shown to be powerful for multi-electron excitation and ionization processes.(3) Chemisorption of an oxygen molecule on a silver surface is studied theoretically with the use of the Dipped Adjuster Model (DAM) for Ag_xO_2 with x = 2 and 4. Electron correlation in low-lying surface states and electron transfer from bulk metal are described by combining DAM with the symmetry-adapted cluster (SAC) CI method. For chemisorption, electron transfer from the bulk metal to the Adjuster and the electrostatic image force are important. They cannot be treated by the conventional cluster model, but are dealt with by the DAM. Three lowlying states, ^2A_1, ^2A_2, and ^2B_1 of the adclusters of Ag_2O_2^- and Ag_4O_2^- are involved in the chemisorption process. In the molecular adsorption state, the ^2A_1 state is assigned to peroxide (O_2^<2->) species and the ^2A_2 and ^2B_1 states to superoxide (O_2^-) species. The 0-0 stretching frequencies are in good agreement with the experimental values. In the potential energy curves of Ag_4O_2^-, another potential minimum corresponding to th e dissociative adsorption state is obtained for the ^2A_1 state. The ener-getics of the molecular and dissociative adsorptions show reasonable agreement with experiments. Less

范德华分子和金属团簇的反应和动力学是最近实验和理论研究的主题。在本研究项目中，我们用量子化学方法对这些课题中的几个主题进行了研究。(1)用SAC/SAC-CI方法研究了Ar_2、Kr_2、ArF和CsRg(Rg=Ne、Ar、Kr、Xe)等Ven der Waals分子的圆态、激发态和电离态的势能曲线。对于Ar_2，4s和4p Rydberg的计算结果与吸收光谱和发射光谱的实验结果符合得很好。给出了观测光谱的一些新的指认，特别是对束缚激发态的激发。对于CsRg体系，SAC-CI势能曲线和(诱导)跃迁矩很好地再现了观察到的碰撞诱导吸收光谱。然后我们可以澄清包括在观察到的碰撞诱导吸收光谱中的详细电子过程。(2)…更多指数生成波函数(EGWF)方法是SAC方法的推广。将激励器方法应用于EGWF方法，是对SAC-CI方法的推广。这些方法适用于C2、CO、HF等各种基态、激发态、电离态和阴离子态在正常和加长距离下的计算，与完整的CI(精确)解符合得很好。结果表明，我们已经准备好了适用于任意核组态的基态、激发态、电离态和阴离子态的理论。(3)用浸渍调节器模型(DAM)对x=2和4的Ag_xO_2分子在银表面的化学吸附进行了理论研究。用DAM和对称适应团簇(SAC)CI方法相结合的方法描述了低激发态的电子关联和块状金属的电子转移。对于化学吸附，从块状金属到调节器的电子转移和静电成像力是重要的。它们不能用传统的集群模型来处理，而是由大坝来处理。Ag_2O_2^-和Ag_4O_2^-团簇的三个低能态：^2A_1、^2A_2和^2B_1参与了化学吸附过程。在分子吸附状态下，^2A1态属于过氧化氢(O2^&lt；2-gt；)物种，^2A2和^2B_1态属于超氧化物(O2^-)物种。0-0伸缩频率与实验值吻合较好。在Ag_4O_2^-的势能曲线中，^2A_1态对应于解离吸附状态的另一个势能极小值。分子吸附和解离吸附的能量学与实验符合得很好。较少

项目成果

H. Nakatsuji: ""Exponentially Generated Configuration Interaction Theory. Descriptions of Excited, Ionized, and Electron Attached States"" J. Chem. Phys.

H. Nakatsuji：“指数生成构型相互作用理论”。

H. Nakatsuji, K. Hirao, and Y. Mizukami: ""SAC-CI and Full-CI calculations for the Singlet and Triplet Excited Excited States of H_2O"" Chem. Phys. Letters.

H. Nakatsuji、K. Hirao 和 Y. Mizukami：“H_2O 的单重态和三重态激发态的 SAC-CI 和 Full-CI 计算”Chem。

H.Nakatsuji,S.Saito: "Theoretical Study for the Excited States of MoO_<4ーn>S^<2ー>_n(n=0ー4) and MoSe^<2ー>_4" J.Chem.Phys.93(3). 1865-1875 (1990)

H.Nakatsuji、S.Saito：“MoO_<4-n>S^<2->_n(n=0-4) 和 MoSe^<2->_4 激发态的理论研究”J.Chem.Phys .93(3)。1865-1875（1990）

H.Nakatsuji,S.Saito: "Theoretical Study for the Excited States of MoO_<4-n>S^<2->_n (n=0-4) and MoSe^<2->_4" J.Chem.Phys.93(3). 1865-1875 (1990)

H.Nakatsuji,S.Saito：“MoO_<4-n>S^<2->_n (n=0-4) 和 MoSe^<2->_4 激发态的理论研究”J.Chem.Phys

H.Nakatsuji: "Theoretical study on Molecular and Dissociative Chemisorption of Oxygen Molecule on an Ag Surface" 発表予定.

H. Nakatsuji：“银表面氧分子的分子和解离化学吸附的理论研究”即将发表。