Is the large molecular deformation in TICTphenomenon really twisting mode?

TICT现象中的大分子变形真的是扭曲模式吗？

• 批准号: 10640500
• 负责人: OKUYAMA Katsuhiko
• 金额: $ 1.73万
• 依托单位: Nihon University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640500/
• 关键词: TICT phenomenon; twisting mode; p-cyanophenylpyrrol; a supersonic-jet laser spectroscopy; an S_0-S_1 electronic transition; TICT state; 394 cm^<-1> vibrational coordinate; vibronic interaction; p-シアノフェニルピロール; ジェット分光; フェニルピロール; 大振幅ねじれ運動ポテンシャル

TICT phenomenon was firstly observed by E. Lipert et al at 1962. The interpretation and nomenclature was carried out by K. Rotkiewicz et al at 1973. Many world-wide scientists have as far confirmed it in many aromatic molecules consisting of donor and acceptor chromophers. Its concept has once seemed to be established. We have, however, thought it doubtful whether the large molecular deformation in TICT phenomenon is really twisting mode, although we could have recognized 'large deformation and charge transfer process' in the interpretation. With help of the Grant-in-Aid for Scientific Research (C)(2), the check investigation has been carried out for two years. Using a supersonic-jet laser spectroscopy we observed the S_0-S_1 electronic transitions of some of representative TICT molecules. The detail analysis of them should lead to the elucidation on the basis of the following idea, the S_1 and TICT states vibronically and mutually interact because of their energetic proximity. As a result, we observed the tangle vibronic pattern, indicating the electronic-state mixing, in the S_0-S_1 electronic transitions of jet-cooled p-cyanophenylpyrrol. The analysis leads to two conclusions,1. Upon the electronic excitation, the dihedral angle between the pyrrol and benzonitrile planes decreases from 39 to 20 degrees.2. Large deformation occurs along the direction in the 394 cm^<-1> vibrational coordinate.The explicit vibronic assignment of the mode has not yet completed and in progress.

TICT现象由E. Lipert等人于1962年首次观察到，并由K. Rotkiewicz等人于1973年进行解释和命名。 迄今为止，许多世界范围内的科学家已经在许多由供体和受体色团组成的芳香分子中证实了这一现象。 。它的概念一度似乎已经确立。然而，尽管我们在解释中可以认识到“大变形和电荷转移过程”，但我们仍然怀疑TICT现象中的大分子变形是否真的是扭曲模式。在科学研究补助金（C）（2）的帮助下，核查调查已进行了两年。使用超音速喷射激光光谱，我们观察到一些代表性 TICT 分子的 S_0-S_1 电子跃迁。对它们的详细分析应该基于以下想法进行阐明：S_1 和 TICT 状态由于它们的能量接近而振动且相互相互作用。结果，我们在喷射冷却的对氰基苯基吡咯的 S_0-S_1 电子跃迁中观察到了缠结振动模式，表明电子态混合。分析得出两个结论：1．在电子激发下，吡咯和苯甲腈平面之间的二面角从39度减小到20度。2．沿394 cm^<-1>振动坐标方向发生较大变形。模态的显式振动分配尚未完成并正在进行中。

项目成果

奥山克彦: "Large-amplitude torsional potentials and the S_2-S_0 electronic spectra of 2-and 6-phenylazulenes"The Journal of Chemical Physics, (アメリカ物理協会誌AIP). (投稿中).

Katsuhiko Okuyama：“2-和 6-苯基薁烯的大振幅扭转势和 S_2-S_0 电子光谱”《化学物理杂志》（AIP）（进行中）。

Katsuhiko OKUYAMA et al.: "Electronic spectra of jet-cooled 1-phenylpyrrole : Large-amplitude torsional motion and twisted intramolecular charge-transfer phenomenon"The Journal of Chemical Physics. 109(17). 7185-7196 (1998)

Katsuhiko OKUYAMA 等人：“喷射冷却 1-苯基吡咯的电子光谱：大振幅扭转运动和扭曲分子内电荷转移现象”《化学物理杂志》。

奥山克彦: "Electronic spectra of jet-cooled 1-phenylpyrrole : large-amplitude torsional motion and twisted intramolecular charge-transfer phenomenon"The Journal of Chemical Physics, (アメリカ物理協会誌AIP). 109(17). 7185-7196 (1998)

Katsuhiko Okuyama：“喷射冷却 1-苯基吡咯的电子光谱：大振幅扭转运动和扭曲分子内电荷转移现象”，化学物理杂志，(AIP) 109(17) (1998)。

Katsuhiko Okuyama: ""Analysis of Electronic Spectra of Jet-Cooled p-Cyanophenylpyrrole:Indirect Evidence of Non-Twisted TICT Phenomenon presented by Supersonic-Jet Laser Spectroscopy""The Journal of Chemical Physics, (米国物理協会). (発表予定). (2000)

Katsuhiko Okuyama：“喷射冷却对氰基苯基吡咯的电子光谱分析：超音速喷射激光光谱法提出的非扭曲 TICT 现象的间接证据”《化学物理学杂志》（美国物理学会）（待提交）。 ）（2000）

Katsuhiko OKUYAMA et al.: "Large-amplitude torsional potentials and the S_2-S_0 electronic spectra of 2- and 6-phenylazulenes"Submitted to The Journal of Chemical.

Katsuhiko OKUYAMA 等人：“2- 和 6-苯基薁烯的大振幅扭转势和 S_2-S_0 电子光谱”提交给《化学杂志》。