Spectroscopic study on excitonic interactions in hydrogen-bonded dusters in the gas phase

气相氢键掸子中激子相互作用的光谱研究

• 批准号: 18350013
• 负责人: SEKIIYA Hiroshi
• 金额: $ 9.87万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18350013/
• 关键词: excitonic interaction; excited-state dynamics; supersonic jet; hydrogen bond; proton transfer; electronic spectrum; fluorescence; tunneling effect; エキシトン; 7-アザインドール2量体; 1-アザカルバゾール2量体; 孤立状態; 分子間振動

It is known that there are two types of excitonic interaction in Frenkel type: One is strong coupling case and the other is weak coupling case. The excitonic interaction in planar hydrogen-bonded dimer and clusters has not been clarified. We have investigated excitonic interactions in the hydrogen-bonded clusters in the gas phase with laser spectroscopic methods. The molecular systems we studied are 7-azaindole dime substituted 7-azaindole dimers (7AI_2), and 1-azacarbazole dimer (1AC_2). We have measured the electronic spectra of isotopomers, undeuterated (hh), one of the NH groups is deuterated (hd) , and the two NH groups are deuterated (dd). In the case of 7AI_2hd the excitation is completely localized on one monomer unit (h *d or hd*) in the lowest excited electronic sate (S_1), indicating that the 7AI_2 in the S_1 state should be classified as a weak coupling case of the exciton theory. The splitting of the zero-point level due to excitonic interaction has been determined to be〜2 cm^<-1>. The excitonic splittings of 4-chloro-7-azaindole dimer and 4-dimethylamino-7-azaindole dimer are predicted to be similar values as 7AI_2. On the other hand, the excitation is not completely localized on one monomer moiety in 1AC_2-hd The difference between 7Al_2 and 1AC_2is due to smaller excitonic splitting in the S_1 state of 1AC_2.

Frenkel型激子相互作用有两种类型：一种是强耦合情况，另一种是弱耦合情况。平面氢键二聚体和团簇中的激子相互作用还不清楚。用激光光谱方法研究了气相中氢键团簇中激子的相互作用。我们所研究的分子体系是7-氮杂吲哚二取代的7-氮杂吲哚二聚体（7AI_2）和1-氮杂咔唑二聚体（1AC_2）。我们已经测量了同位素异构体的电子光谱，未氘化的（hh），一个NH基团是氘代的（hd），和两个NH基团是氘代的（dd）。7AI_2hd在最低激发电子态（S_1）时，激发完全局域在一个单体单元（h *d或hd*）上，表明处于S_1态的7AI_2属于激子理论的弱耦合情况。激子相互作用导致的零点能级的分裂已被确定为1.2 cm-1<-1>。4-氯-7-氮杂吲哚二聚体和4-二甲氨基-7-氮杂吲哚二聚体的激子分裂值与7Al_2相近。7Al_2和1AC_2之间的差异是由于1AC_2的S_1态激子分裂较小。

项目成果

Heavy mass effect on excited-state double-proton transfer in the 7-azaindole dimer induced by Cl substitution

Cl取代诱导的7-氮杂吲哚二聚体中激发态双质子转移的重质量效应

• 发表时间: 2007
• 期刊: Chemical Physics Letters 441
• 作者: X.Zhang;et. al.
• 通讯作者: et. al.

Cooperative triple-proton/hydrogen atom relay in 7-azaindole(CH3OH)2 in the gas phase: remarkable change in the reaction mechanism from vibrational-mode specific to statistical fashion with increasing internal energy.

• DOI: 10.1021/jp070359a
• 发表时间: 2007-05
• 期刊: The journal of physical chemistry. A
• 作者: Kenji Sakota;N. Inoue;Y. Komoto;H. Sekiya

Mechanism of excited-state doulble-proton transfer in the 7-azaindole dimer as a model DNA base pair revealed by frequency- and time-resolved

频率和时间分辨揭示 7-氮杂吲哚二聚体中作为模型 DNA 碱基对的激发态双质子转移机制

• 发表时间: 2008
• 期刊: J.Photochem.Photobiol.C-Photochem Reviews (印刷中)(In press)
• 作者: Y. Yasaka;C. Wakai;N. Matubayasid;M. Nakahara;H.Sekiya and K.Sakota
• 通讯作者: H.Sekiya and K.Sakota

塩基対の光誘起ダブルプロトン移動のメカニズム

光诱导碱基对双质子转移机制

• 发表时间: 2006
• 期刊: 固体物理(新しい水素の科学特集号) 41
• 作者: 関谷 博;迫田 憲治
• 通讯作者: 迫田 憲治

Spectroscopic studies on multi-proton/hydrogen transfer reactions in the 7-azaindole dimer and hydrated clusters of 7-azaindole

7-氮杂吲哚二聚体和7-氮杂吲哚水合簇中多质子/氢转移反应的光谱研究

• 发表时间: 2008
• 作者: H.Sekiya;et. al.
• 通讯作者: et. al.