Conformer-Specific Tunneling Dynamics Dictated by the Seam Coordinate of the Conical Intersection

Cited 0 time in webofscience Cited 0 time in scopus
  • Hit : 27
  • Download : 0
The dynamic role of the conical intersection "seam" coordinate has been first revealed in the H fragmentation reaction of ortho(o)-cresol conformers. One of the (3N - 8) dimensional seam coordinates of the S-1(pi pi*)/S-2(pi sigma*) conical intersection has been identified as the CH3 torsional potential function. The tunneling dynamics of the reactive flux is dictated by its nuclear layout with respect to the CH3 torsional angle, as the multidimensional tunneling barrier is dynamically shaped along the conical intersection seam. The effective tunneling-barrier weight-averaged over the quantum-mechanical probability along the CH3 torsional angle perfectly explains the experimental finding: the sharp variation of the tunneling rate ((700-400) ps(-1)) with the CH3 torsional mode excitations within the narrow (0-100 cm(-1)) energetic window. The much longer S-1 lifetime of cis compared to trans is ascribed to the higher-lying S-1/S-2 conical intersection of the former. With the use of distinct lifetimes, vibronic bands of each conformer could be completely separated.
Publisher
AMER CHEMICAL SOC
Issue Date
2021-02
Language
English
Article Type
Article
Citation

JOURNAL OF PHYSICAL CHEMISTRY LETTERS, v.12, no.7, pp.1854 - 1861

ISSN
1948-7185
DOI
10.1021/acs.jpclett.0c03742
URI
http://hdl.handle.net/10203/282390
Appears in Collection
CH-Journal Papers(저널논문)
Files in This Item
There are no files associated with this item.

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0