Revealing Transition State Signatures in Collisional Vibrational Quenching Aided by Conical Intersections
We dissect the dynamics of vibrational quenching of HBr by collisions with atomic iodine, which are affected by conical intersections in the strongly interacting regions. Trajectory surface hopping calculations using a newly developed ab initio-based diabatic potential energy matrix reveal that the vibrational inelasticity stems largely from a "frustrated reaction" mechanism, in which the trajectories access the vicinity of a reactive transition state where intermodal coupling is strong. This is aided by nonadiabatic transitions near conical intersections. In addition, the vibration-rotation energy transfer leads to a forward scattering bias, following a hard collision glory scattering mechanism, facilitated by a delicate counterbalance between attractive and repulsive forces.
Authors
- Xixi Hu (ORCID: https://orcid.org/0000-0003-1530-3015)
- Weigao Xu (ORCID: https://orcid.org/0000-0002-3014-756X)
- Qixin Chen (ORCID: https://orcid.org/0000-0002-1768-8732)
- Hua Guo (ORCID: https://orcid.org/0000-0001-9901-053X)
- Shanyu Han (ORCID: https://orcid.org/0000-0001-5482-6658)
- Daiqian Xie (ORCID: https://orcid.org/0000-0001-7185-7085)
- Feng An (ORCID: https://orcid.org/0000-0002-7617-2402)
- Hanzi Zhang
Institutions
- Allen Institute for Brain Science (US)
- University of New Mexico (US)
- Zhejiang Lab (CN)
- Mineral Resources (AU)
- Computational Physics (United States) (US)
- Hongzhiwei Technology (China) (CN)
- Ministry of Education and Child Care (CA)
- Nanjing University (CN)
Publication Details
- Journal
- The Journal of Physical Chemistry Letters
- Published
- 2025-07-19
- DOI
- https://doi.org/10.1021/acs.jpclett.5c01196
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China
- Nanjing University