Laser spectroscopic study of intracluster chemical reactions

簇内化学反应的激光光谱研究

• 批准号: 05403004
• 负责人: MIKAMI Naohiko
• 金额: $ 25.02万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05403004/
• 关键词: Molecular Clusters; Intracluster Reactions; Hydrogen Bonded Clusters; Vibrational Spectroscopy of Molecular Clusters; フェノール・水クラスター; クラスター振動分光; IR-UV二重共鳴分光; 分子クラスター内反応; 分子クラスター構造; クラスターの赤外分光

1. Spectroscopic studies of the hydrogen-bonding clusters of phenol were reviewed with an emphasis of the characterization of the cluster structures involving the proton transfer processes. Two experimental methods which were newly developed for the spectroscopy of the size selected clusters and their ions were described. Trapped ion photodissociation spectroscopy revealed that chromophore alternation occurs in the cluster cations with various proton-accepting molecules, such as NH_3 and H_2O.The infrared spectroscopy combined with the ionization detection was applied to the spectra of the OH vibrations which characterized the neutral clusters of phenol with water. The spectroscopic evidence of the ion-pair form of the neutral cluster is presented and the possibility of the intracluster acid-base reaction is discussed.2. The OH stretching vibrations of the phenol dimer and trimer prepared in supersonic jets have been observed by IR-UV double-resonance and stimulated Raman-UV double-resonance spectroscopies. In the trimer, all the three OH stretching vibrations showed large red shifts from that of bare phenol. Evidence of the cyclic structure was obtained from an intensity alternation between IR and Raman spectra and by the measurement of the Raman depolarization ratios. In the dimer, it was found that the IR intensity of the OH stretching vibration of the proton-donating phenol is 4 times larger than that of the proton-accepting phenol.

1. 综述了苯酚氢键簇的光谱研究，重点介绍了涉及质子转移过程的簇结构的表征。描述了两种新开发的用于选定尺寸簇及其离子的光谱的实验方法。俘获离子光解光谱表明，NH_3和H_2O等各种接受质子的分子簇中的阳离子发生发色团交替。红外光谱与电离检测相结合，应用于表征苯酚与水的中性簇的OH振动光谱。给出了中性团簇离子对形式的光谱证据，并讨论了团簇内酸碱反应的可能性。 2．通过红外-紫外双共振和受激拉曼-紫外双共振光谱观察了超声喷射制备的苯酚二聚体和三聚体的OH伸缩振动。在三聚体中，所有三个 OH 伸缩振动均显示出与裸苯酚相比较大的红移。环状结构的证据是通过红外光谱和拉曼光谱之间的强度交替以及拉曼消偏振比的测量获得的。在二聚体中，发现供质子苯酚的OH伸缩振动的IR强度比接受质子苯酚的OH伸缩振动的IR强度大4倍。

项目成果

Naohiko Mikami: "Spectriscopic Study of Intracluster Proton Transter in Small Size Hydrogen-Bonding Clusters of Phenol" Bull. Chem. Soc. Jpn.68. 683-695 (1995)

Naohiko Mikami：“小尺寸苯酚氢键簇内簇内质子转移的光谱研究”公牛。

Ken Takazawa: "Internal rotation of the methyl group in fluorotoluene cations as studied by pulsed field ionization-zero kinetic energy spectroscopy" J.Chem.Phys.99. 3205-3217 (1993)

Ken Takazawa：“通过脉冲场电离-零动能光谱研究氟甲苯阳离子中甲基的内部旋转”J.Chem.Phys.99。

Shin Sato: "Electronic Spectra of Jet-Cooled Cations of Hydrogen-bonded Complexes of Phenol" Spectrochimica Acta. 50A. 1413-1419 (1994)

Shin Sato：“苯酚氢键配合物的喷射冷却阳离子的电子光谱”光谱化学学报。

Takayuki Ebata: "Evidence for the Cyclic Form of Phenol Trimer : Vibrational Spectroscopy of the OH Stretching Vibrations of Jet-Cooled Phenol Dimer and Trimer" J. Phys. Chem.66. 5761-5764 (1995)

Takayuki Ebata：“苯酚三聚体环状形式的证据：喷射冷却苯酚二聚体和三聚体的 OH 拉伸振动的振动光谱”J. Phys。

Shin Sato: "Electronic spectra of jet-cooled cations of hydrogenbonded complexes of phenol" Spectrochim.Acta. 50A. 1413-1419 (1994)

Shin Sato：“苯酚氢键配合物的喷射冷却阳离子的电子光谱”Spectrochim.Acta。