Rotational Modulation of ò A"-State Photodissociation of HCO via Renner-Teller Nonadiabatic Transitions
Abstract
By examining the product-state distribution of a prototypical nonadiabatic predissociation system, HCO(Ã2 A"-X̃2A′), we demonstrate that the dissociation dynamics is strongly modulated by parent rotational quantum numbers. The predissociation of the nominal (νC-H= 0, νbend, νC-O= 1) vibronic levels of the Ã2A" 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 νC-O= 0. This unique phenomenon is a purely quantum mechanical behavior that has no classical analogue.
Recommended Citation
S. Han et al., "Rotational Modulation of ò A"-State Photodissociation of HCO via Renner-Teller Nonadiabatic Transitions," Journal of Physical Chemistry Letters, vol. 12, no. 28, pp. 6582 - 6588, American Chemical Society (ACS), Jul 2021.
The definitive version is available at https://doi.org/10.1021/acs.jpclett.1c01932
Department(s)
Chemistry
International Standard Serial Number (ISSN)
1948-7185
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2021 American Chemical Society (ACS), All rights reserved.
Publication Date
22 Jul 2021
PubMed ID
34242507
Comments
This research was supported by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences (Grant Nos. DE-SC0015997 to H.G. and DE-SC0019740 to R.D.) and by the U.S. National Science Foundation (Grant No. CHE-1566636 to J.Z.).