Title

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.

Department(s)

Chemistry

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.).

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

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