The vibronic state dependent predissociation of H2S: Determination of all fragmentation processes

Y.R. Zhao, J.J. Chen, Z.J. Luo, Y. Chang, J.Y. Yang, W.Q. Zhang, G.R. Wu, S.W. Crane, C.S. Hansen, H.B. Ding, F. An, X.X. Hu, D.Q. Xie, Michael N R Ashfold*, K.J. Yuan*, X.M. Yang

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

8 Citations (Scopus)

Abstract

Photochemistry plays a significant role in shaping the chemical reaction network in the solar nebula and interstellar clouds. However, even in a simple triatomic molecule photodissociation, determination of all fragmentation processes is yet to be achieved. In this work, we present a comprehensive study of the photochemistry of H2S, derived from cutting-edge translational spectroscopy measurements of the H, S(1D) and S(1S) atom products formed by photolysis at wavelengths across the range 155–120 nm. The results provide detailed insights into the energy disposal in the SH(X), SH(A) and H2 co-fragments, and the atomisation routes leading to two H atoms along with S(3P) and S(1D) atoms. Theoretical calculations allow the dynamics of all fragmentation processes, especially the bimodal internal energy distributions in the diatomic products, to be rationalised in terms of non-adiabatic transitions between potential energy surfaces of both 1A′ and 1A′′ symmetry. The comprehensive picture of the wavelength-dependent (or vibronic state-dependent) photofragmentation behaviour of H2S will serve as a text-book example illustrating the importance of non-Born–Oppenheimer effects in molecular photochemistry, and the findings should be incorporated in future astrochemical modelling.

Original languageEnglish
Pages (from-to)2501-2517
Number of pages17
JournalChemical Science
Volume14
Issue number10
DOIs
Publication statusPublished - 14 Feb 2023

Bibliographical note

Funding Information:
This work was supported by the National Natural Science Foundation of China (NSFC Center for Chemical Dynamics (Grant No. 22288201)), the National Natural Science Foundation of China (Grant No. 22241304, 22073042, 22122302, 22225303, 22233003), the Key Technology Team of the Chinese Academy of Sciences (Grant No. GJJSTD20220001), the Innovation Program for Quantum Science and Technology (2021ZD0303304), the Liaoning Revitalization Talents Program (Grant No. XLYC1907154). CSH is grateful for funding from the Australian Research Council (ARC, DE200100549). MNRA and SWC are grateful for funding from the Engineering and Physical Sciences Research Council (EPSRC, EP/L005913). MNRA and CSH are grateful to the NSFC Center for Chemical Dynamics for the award of Visiting Fellowships and MNRA, SWC and CSH are very grateful to the late Dr Colin Western (Bristol) for many helpful discussions in the early stages of this collaboration. We are grateful to the High Performance Computing Center (HPCC) of Nanjing University for running the ab initio calculations on its blade cluster system.

Publisher Copyright:
© 2023 The Royal Society of Chemistry.

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