Multiple Dissociation Pathways in HNCO Decomposition Governed by Potential Energy Surface Topography

Zhang, Zhiguo1,2,3; Wu, Hao1,4; Chen, Zhichao1; Fu, Yanlin1; Fu, Bina1,4,5; Zhang, Dong H.1,4,5; Yang, Xueming1,4,5,6,7; Yuan, Kaijun1,4,5

2023-09-01

10.1021/jacsau.3c00414

JACS AU   Impact Factor & Quartile

2691-3704

The exquisite features of molecular photochemistry are key to any complete understanding of the chemical processes governed by potential energy surfaces (PESs). It is well established that multiple dissociation pathways relate to nonadiabatic transitions between multiple coupled PESs. However, little detail is known about how the single PES determines reaction outcomes. Here we perform detailed experiments on HNCO photodissociation, acquiring the state-specific correlations of the NH (a(1)Delta) and CO (X-1 Sigma(+)) products. The experiments reveal a trimodal CO rotational distribution. Dynamics simulations based on a full-dimensional machine-learning-based PES of HNCO unveil three dissociation pathways exclusively occurring on the S-1 excited electronic state. One pathway, following the minimum energy path (MEP) via the transition state, contributes to mild rotational excitation in CO, while the other two pathways deviating substantially from the MEP account for relatively cold and hot CO rotational state populations. These peculiar dynamics are unambiguously governed by the S-1 state PES topography, i.e., a narrow acceptance cone in the vicinity of the transition state region. The dynamical picture shown in this work will serve as a textbook example illustrating the importance of the PES topography in molecular photochemistry.

State-resolved photodissociation multiple dissociationpathways potential energy surface excited states quasi-classical dynamics

ESCI

English

Others

National Natural Science Foundation of China[GJJSTD20220001] ; Scientific Instrument Developing Project of the Chinese Academy of Sciences[2021ZD0303304] ; Innovation Fund Project of Dalian Institute of Chemical Physics[SKLMRD-K202313] ; Open Foundation of State Key Laboratory[2021ZD0303305] ; Innovation Program for Quantum Science and Technology[2021RD05] ; Dalian Innovation Support Program["2019ZT08L455","2019JC01091"] ; Guangdong Science and Technology Program[ZDSYS20200421111001787] ; Shenzhen Science and Technology Program[2023AH050426]

Chemistry

Chemistry, Multidisciplinary

WOS:001071378600001

AMER CHEMICAL SOC

Web of Science

1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam & Dalian Coherent Li, Dalian 116023, Peoples R China
2.Fuyang Normal Univ, Key Lab Funct Mat & Devices Informat Anhui Educ In, Fuyang 236037, Anhui, Peoples R China
3.Fuyang Normal Univ, Sch Phys & Elect Engn, Fuyang 236041, Anhui, Peoples R China
4.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
5.Hefei Natl Lab, Hefei 230088, Peoples R China
6.Southern Univ Sci & Technol, Coll Sci, Dept Chem, Shenzhen 518055, Peoples R China
7.Southern Univ Sci & Technol, Coll Sci, Ctr Adv Light Source Res, Shenzhen 518055, Peoples R China

Zhang, Zhiguo,Wu, Hao,Chen, Zhichao,et al. Multiple Dissociation Pathways in HNCO Decomposition Governed by Potential Energy Surface Topography[J]. JACS AU,2023.

Zhang, Zhiguo.,Wu, Hao.,Chen, Zhichao.,Fu, Yanlin.,Fu, Bina.,...&Yuan, Kaijun.(2023).Multiple Dissociation Pathways in HNCO Decomposition Governed by Potential Energy Surface Topography.JACS AU.

Zhang, Zhiguo,et al."Multiple Dissociation Pathways in HNCO Decomposition Governed by Potential Energy Surface Topography".JACS AU (2023).