Hydroxyl super rotors from vacuum ultraviolet photodissociation of water

• Published in: Nature communications Vol. 10; no. 1; p. 1250
• Main Authors: Chang, Yao, Yu, Yong, Wang, Heilong, Hu, Xixi, Li, Qinming, Yang, Jiayue, Su, Shu, He, Zhigang, Chen, Zhichao, Che, Li, Wang, Xingan, Zhang, Weiqing, Wu, Guorong, Xie, Daiqian, Ashfold, Michael N. R., Yuan, Kaijun, Yang, Xueming
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 19.03.2019; Nature Publishing Group; Nature Portfolio
• Subjects: 140/125; 639/33; 639/638; 639/638/440/949; Adiabatic; Bending vibration; Energy of dissociation; Free energy; Free radicals; Heat of formation; Humanities and Social Sciences; Hydroxyl radicals; Internal conversion; Internal energy; Interstellar matter; multidisciplinary; Photodissociation; Photolysis; Rotors; Science; Science (multidisciplinary); Theoretical analysis; Ultraviolet radiation; Vacuum; Vibration analysis; Water chemistry
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-019-09176-z

Hydroxyl radicals (OH) play a central role in the interstellar medium. Here, we observe highly rotationally excited OH radicals with energies above the bond dissociation energy, termed OH “super rotors”, from the vacuum ultraviolet photodissociation of water. The most highly excited OH( X ) super rotors identified at 115.2 nm photolysis have an internal energy of 4.86 eV. A striking enhancement in the yield of vibrationally-excited OH super rotors is detected when exciting the bending vibration of the water molecule. Theoretical analysis shows that bending excitation enhances the probability of non-adiabatic coupling between the B ̃ and X ̃ states of water at collinear O–H–H geometries following fast internal conversion from the initially excited D ̃ state. The present study illustrates a route to produce extremely rotationally excited OH( X ) radicals from vacuum ultraviolet water photolysis, which may be related to the production of the highly rotationally excited OH( X ) radicals observed in the interstellar medium. Free electron lasers provide a state-of-the-art tool to investigate the photochemistry of water. Here, the authors show that highly rotationally excited hydroxyl radicals, so-called “super rotors” existing above the bond dissociation energy, are observed from the photodissociation of water, which may have implications for understanding the interstellar medium.