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Title: Nonadiabatic Electronic Energy Transfer in Chemical Oxygen-Iodine Laser: Powered by Derivative Coupling or Spin-Orbit Coupling?

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [1];  [1];  [2];  [1]
  1. Nanjing Univ. (China)
  2. Univ. of New Mexico, Albuquerque, NM (United States)
+ Show Author Affiliations

Derivative couplings near a conical intersection and spin-orbit couplings between different spin states are known to facilitate nonadiabatic transitions in molecular systems. In this report, we investigate a prototypical electronic energy transfer process, I(2P3/2)+O2(a1Δg)→I(2P1/2)+ O2(X3Σg-), which is of great importance for the chemical oxygen-iodine laser. To understand the nonadiabatic dynamics, this multistate process is investigated in full dimensionality with quantum wave packets using diabatic potential energy surfaces coupled by both derivative and spin-orbit couplings, all determined from first principles. A near quantitative agreement with structural, energetic, and kinetic measurements is achieved. Detailed analyses suggest that the nonadiabatic dynamics is largely controlled by derivative coupling near conical intersections, which leads to a small effective barrier and hence a slightly positive temperature dependence of the rate coefficient. The new findings should extend our understanding of energy transfer, provide a quantitative basis for numerical simulations of the chemical oxygen-iodine laser, and have important implications in other electronic energy transfer processes.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Natural Science Foundation of China (NSFC); Chinese Ministry of Science and Technology
Grant/Contract Number:
SC0015997
OSTI ID:
1630488
Journal Information:
Journal of Physical Chemistry Letters, Vol. 11, Issue 12; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
potential energy surface
laser chemistry
nonadiabatic dynamics
conical intersection
spin-orbit coupling
quantum wave packet