Quenching of Charge Transfer in Nitrobenzene Induced by Vibrational Motion

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• 作者：J. Patrick Zobel ; Juan J. Nogueira ; Leticia Gonz谩lez
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2015
• 出版时间：August 6, 2015
• 年：2015
• 卷：6
• 期：15
• 页码：3006-3011
• 全文大小：330K
• ISSN：1948-7185

文摘

Although nitrobenzene is the smallest nitro-aromatic molecule, the nature of its electronic structure is still unclear. Most notably, the lowest-energy absorption band was assessed in numerous studies providing conflicting results regarding its charge-transfer character. In this study, we employ a combination of molecular dynamics and quantum chemical methods to disentangle the nature of the lowest-energy absorption band of nitrobenzene. Surprisingly, the charge-transfer transition from the benzene moiety to the nitro group is found to be quenched by a flow of charge into the opposite direction induced by vibrational motion. Beyond clarifying the charge-transfer character of nitrobenzene, we show that the widely used approach of analyzing the ground-state minimum-energy geometry provides completely wrong conclusions.