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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Near-UV resonant two-photon ionization spectroscopy of gas phase guanine: Evidence for the observation of three rare tautomers
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Near-UV resonant two-photon ionization spectroscopy of gas phase guanine: Evidence for the observation of three rare tautomers

机译：气相鸟嘌呤的近紫外共振双光子电离光谱：观察三种稀有互变异构体的证据

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摘要

In light of a recently published study on the IR spectroscopy of guanine in He droplets (Choi, M. Y.; Miller, R. E. J. Am. Chem. Soc. 2006, 128, 7320), the present letter proposes a new interpretation of the resonant two-photon ionization (R2PI) experiments on gas phase guanine, which is supported by quantum chemistry calculations. Whereas He droplet experiments detect the most stable forms, only one of these forms is observed (very marginally) in the R2PI spectrum, which is actually dominated by three less stable "rare" tautomers, whose stabilities lie in the 3-7 kcal/mol range. The absence of the most stable forms in the R2PI spectrum suggests that a tautomer-dependent ultrafast relaxation process takes place in the excited state of these stable tautomers. The present reinterpretation modifies qualitatively the picture of the excited state of guanine tautomers and should contribute to the understanding of the deactivation mechanisms taking place in the excited state of DNA bases.
机译：鉴于最近发表的有关He液滴中鸟嘌呤的红外光谱研究（Choi，MY; Miller，REJ Am。Chem。Soc。2006，128，7320），本信提出了共振双光子的新解释。气相鸟嘌呤的电离（R2PI）实验，这得到了量子化学计算的支持。尽管He液滴实验检测到最稳定的形式，但在R2PI光谱中仅观察到这些形式中的一种（非常微弱），实际上是由三个稳定性较差的“稀有”互变异构体所控制，其稳定性在3-7 kcal / mol范围。 R2PI光谱中没有最稳定的形式，这表明依赖互变异构体的超快弛豫过程是在这些稳定互变异构体的激发态发生的。目前的重新解释从质量上改变了鸟嘌呤互变异构体的激发态图，并应有助于理解DNA碱基的激发态发生的失活机理。

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