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Title: Rotational Modulation of $Ã^2A''$-State Photodissociation of HCO via Renner–Teller Nonadiabatic Transitions

Journal Article · · Journal of Physical Chemistry Letters
 [1]; ORCiD logo [2];  [3];  [2]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States)
  2. Univ. of California, Riverside, CA (United States)
  3. Univ. of California, Riverside, CA (United States); Anhui Normal Univ., Wuhu (China)
  4. Missouri Univ. of Science and Technology, Rolla, MO (United States)
  5. Nanjing Univ. (China)
  6. Department of Chemistry, University of California Riverside, Riverside, California 92521, United States
+ Show Author Affiliations

By examining the product-state distribution of a prototypical non- adiabatic predissociation system, HCO($$Ã^2A''–\tilde X^2A'$$), we demonstrate here that the dissociation dynamics is strongly modulated by parent rotational quantum numbers. The predissociation of the nominal ($$ν_{\text{C–H}} = 0, ν_{\text{bend}}, ν_{\text{C–O}} = 1$$) vibronic levels of the $AÃ^2A''$ state surprisingly gives rise to both vibrational ground and excited states of the CO product, despite the assumed spectator nature of the CO moiety. This anomaly is attributed to the dependence of the lifetime of the vibronic resonance facilitated by the Renner–Teller interaction on the parent rotational angular momentum quantum numbers coupled with transient intensity borrowing from nearby vibronic resonances with $$ν_{\text{C–O}} = 0$$. This unique phenomenon is a purely quantum mechanical behavior that has no classical analogue.

Research Organization:
Missouri Univ. of Science and Technology, Rolla, MO (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Alexander von Humboldt Foundation; National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China
Grant/Contract Number:
SC0019740; SC0015997; CHE-566636; 21733006; 2017YFA0206500; GXXT 2020-004
OSTI ID:
1864696
Alternate ID(s):
OSTI ID: 1864691
Journal Information:
Journal of Physical Chemistry Letters, Vol. 12, Issue 28; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Wave function
Quantum mechanics
Dissociation
Photodissociation
Energy