Observation of OH stretching vibrations of hydrogen-bonded molecular clusters

氢键分子簇OH伸缩振动的观察

• 批准号: 07454144
• 负责人: EBATA Takayuki
• 金额: $ 4.99万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454144/
• 关键词: hydrogen-bond; clusters; OH stretching vibration; supersonic jet; double resonance; phenol; vibrational relaxation; クラスター; 赤外スペクトル; ラマンスペクトル

The OH stretching vibrations of size-selected hydrogen-bonded clusters of aryl alcohols were observed in supersonic jets. Two spectroscopic methods were applied ; IR-UV double resonance and stimulated Raman-UV double resonance spectroscopies. The investigated hydrogen-bonded systems are phenol-(H_2O)_n, naphthol-(H_2O)_n, tropolone-(H_2O)_n, and also the clusters with other base molecules.In phenol-(H_2O)_n clusters (n=1-5), not only ^vOH of the phenol site but also of the water sites were observed. The cluster structures were investigated by comparing the observed spectra with the ones obtained by ab initio molecular orbital calulation. It was found that ring form hydrogen-bonded structure is most stable for the clusters with 2<less than or equal>n<less than or equal>4, and for larger size clusters, isomers different from the ringstructure seems to becomestable. The OH stretching spectra of naphthol-(H_2O)_n clusters are essentially the same with those of phenol-(H_2O)_n and a similar cluster structures are suggested. It was also found that the relaxation rate of the hydrogen bonded ^vOH are much larger than that of ^vOH free from the hydrogen bondThe decrease of ^vOH frequency by the hydrogen-bond formation versus the strength of basicity was investigated nad it was found the increase shows good correlation with the proton affinity of the base molecules.

在超音速射流中观察到选定尺寸的芳醇氢键簇的 OH 伸缩振动。应用了两种光谱方法；红外-紫外双共振和受激拉曼-紫外双共振光谱。研究的氢键体系有苯酚-(H_2O)_n、萘酚-(H_2O)_n、托酚酮-(H_2O)_n以及与其他基础分子的团簇。在苯酚-(H_2O)_n团簇(n=1- 5)，不仅观察到苯酚位点的^vOH，还观察到水位点的^vOH。通过将观察到的光谱与从头算分子轨道计算获得的光谱进行比较来研究簇结构。研究发现，对于2<小于或等于>n<等于>4的团簇，环状氢键结构最稳定，而对于较大尺寸的团簇，与环结构不同的异构体似乎变得稳定。萘酚-(H_2O)_n簇的OH伸缩光谱与苯酚-(H_2O)_n的OH伸缩光谱基本相同，并暗示了相似的簇结构。还发现氢键^vOH的弛豫速率远大于不含氢键的^vOH。研究了氢键形成对^vOH频率的降低与碱性强度的关系，发现增加表明与基础分子的质子亲和力有良好的相关性。

项目成果

H.Kojima: "Laser-induced fluorescence of jet-cooled chlorotoluene molecules" J.Photochem.Photobiol.A:Chem.,. 92. 1-5 (1995)

H.Kojima：“喷射冷却氯甲苯分子的激光诱导荧光”J.Photochem.Photobiol.A:Chem.,。

Akira Mistuzuka, Asuka Fujii, Takayuki Ebata and Naohiko Mikami: ""Infrared spectroscopy of OH stretching vibrations of hydrogen-bonded tropolone-(H_2O)_n(n=1-3)and tropolone-(CH_3OH)_n(n=1and2) clusters"" J.Chem.Phys.105. 2618-2627 (1996)

Akira Mistuzuka、Asuka Fujii、Takayuki Ebata 和 Naohiko Mikami：“氢键托酚酮-(H_2O)_n(n=1-3)和托酚酮-(CH_3OH)_n(n=1and2)簇的 OH 伸缩振动的红外光谱

A.Mitsuzuka: "Infrared spectroscopy of OH stretching vibrations of hydrogen-bonded tropolone-(H_2O)_n(n=1-3)and tropolone-(CH_3OH)_n(n=1and2)clusters" J.Chem.Phys.105・7. 2618-2627 (1996)

A.Mitsuzuka：“氢键托酚酮-(H_2O)_n(n=1-3)和托酚酮-(CH_3OH)_n(n=1and2)簇的OH伸缩振动的红外光谱” J.Chem.Phys.105・7. 2618-2627 (1996)

T.Ebate: "OH Stretching vibrations of phenol-(H_2O)_1 and phenol-(H_2O)_3 in the S_1 state" J.Phys.Chem.100・2. 546-550 (1996)

T.Ebate：“S_1状态下苯酚-(H_2O)_1和苯酚-(H_2O)_3的OH伸缩振动”J.Phys.Chem.100・2(1996)。

Takayuki Ebata, Akihiro Okazaki, Yoshiya Inokuchi and Naohiko Mikami: ""Degenerate four-wave mixing and two-color laser induced grating spectra of S_1-S_0 electronic transitions of benzene and monosubstituted benzenes in the gas phase"" J.Mol.Structure. 3

Takayuki Ebata、Akihiro Okazaki、Yoshiya Inokuchi 和 Naohiko Mikami：“气相中苯和单取代苯的 S_1-S_0 电子跃迁的简并四波混合和两色激光诱导光栅光谱”J.Mol.Structure。