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Unimolecular Dissociation Dynamics of Electronically Excited Hco(Ã2a′′): Rotational Control of Nonadiabatic Decay
Faraday Discussions
  • Ge Sun
  • Shanyu Han
  • Xianfeng Zheng
  • Yu Song
  • Yuan Qin
  • Richard Dawes, Missouri University of Science and Technology
  • Daiqian Xie
  • Jingsong Zhang
  • Hua Guo
Abstract

The photoinduced unimolecular decay of the electronically excited HCO(Ã2A′′) is investigated in a combined experimental-theoretical study. The molecule is excited to the (1, n2, 0) combination bands, which decay via Renner-Teller coupling to the ground electronic state. The rovibrational state distribution of the CO fragment was measured via the high-n Rydberg H-atom time-of-flight method and calculated using a wave packet method on an accurate set of potential energy surfaces. It is shown that the non-adiabatic decay rate is strongly modulated by the HCO rotational angular momentum, which leaves unique signatures in the product state distribution. The experimentally observed bimodal rotational distribution of the dominant CO(v = 0) fragment is likely due to decay of different vibronic states populated by the excitation and modulated by the excited state lifetime, which is in turn controlled by the parent rotational quantum number.

Department(s)
Chemistry
Comments
National Science Foundation, Grant GXXT 2020-004
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2023 Royal Society of Chemistry, All rights reserved.
Publication Date
3-24-2022
Publication Date
24 Mar 2022
PubMed ID
35781478
Citation Information
Ge Sun, Shanyu Han, Xianfeng Zheng, Yu Song, et al.. "Unimolecular Dissociation Dynamics of Electronically Excited Hco(Ã2a′′): Rotational Control of Nonadiabatic Decay" Faraday Discussions Vol. 238 (2022) p. 236 - 248 ISSN: 1364-5498; 1359-6640
Available at: http://works.bepress.com/richard_dawes/156/