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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >The Ground- and Excited-State (n#pi# and #pi##pi#) Carboxylic Acid-Catalyzed Proton (Hydrogen Atom)-Transfer Energy Surfaces in 3-Formyl-7-azaindole
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The Ground- and Excited-State (n#pi# and #pi##pi#) Carboxylic Acid-Catalyzed Proton (Hydrogen Atom)-Transfer Energy Surfaces in 3-Formyl-7-azaindole

机译：3-甲酰基-7-氮杂吲哚的基态和激发态（n＃pi＃和＃pi ## pi＃）由羧酸催化的质子（氢原子）转移能量表面

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摘要

Theoretical approaches on the ground- and excited-state proton (or hydrogen atom) transfer in the 3-formyl-7-azaindole (3FAI)/formic acid dual hydrogen-bonded complex were performed. In the ground state, the analysis of the transition-state geometry led us to conclude a concerted, asynchronous proton-transfer pattern that correlates with the hydrogen-bonding strength. The lowest singlet excited state in the 3FAI/formic acid complex was calculated to be in an n#pi# configuration. On the basis of frontier molecular orbital analyses, the n -> #pi# transition was concluded to originate from the carbonyl lone-pair electrons of the formyl substitute. A highly endergonic proton-transfer reaction barrier of approx 16.7 kcal/mol was calculated in the n#pi# state at the CIS/6-31G(d',p') level of theory. The second excited singlet state possesses a #pi##pi# configuration in which the excited-state double proton transfer (ESDPT) takes place with a negligible energy barrier. The results provide a theoretical rationalization of the competitive internal conversion/ESDPT mechanism previously proposed for the 3FAI hydrogen-bonded complexes (J. Phys. Chem. A 2000, 104, 8863).
机译：对3-甲酰基-7-氮杂吲哚（3FAI）/甲酸双氢键复合物中的基态和激发态质子（或氢原子）转移进行了理论研究。在基态下，对过渡态几何结构的分析使我们得出了与氢键强度相关的协调一致的异步质子转移模式。计算出3FAI /甲酸复合物中最低的单重态激发态为n＃pi＃构型。根据前沿分子轨道分析，得出n->＃pi＃跃迁源自甲酰基取代基的羰基孤对电子。在理论CIS / 6-31G（d'，p'）的n＃pi＃状态下计算出约16.7 kcal / mol的高负电子质子转移反应势垒。第二个激发单重态具有＃pi ## pi＃构型，其中激发态双质子转移（ESDPT）发生时的能垒可忽略不计。结果为先前提出的用于3FAI氢键配合物的竞争性内部转化/ ESDPT机制提供了理论上的合理化（J. Phys。Chem。A 2000，104，8863）。

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