Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory
Abstract
UV excitation of the CH2OO Criegee intermediate across most of the broad span of the (B 1A') – (X 1A') spectrum results in prompt dissociation to two energetically accessible asymptotes: O (1D) + H2CO (X 1A1) and O (3P) + H2CO (a 3A"). Dissociation proceeds on multiple singlet potential energy surfaces that are coupled by two regions of conical intersection (CoIn). Velocity map imaging (VMI) studies reveal a bimodal total kinetic energy (TKER) distribution for the O (1D) + H2CO (X 1A1) products with the major and minor components accounting for ca. 40% and ca. 20% on average of the available energy (Eavl), respectively. The unexpected low TKER component corresponds to highly internally excited H2CO (X 1A1) products accommodating ca. 80% of Eavl. Full dimensional trajectory calculations suggest that the bimodal TKER distribution of the O (1D) + H2CO (X 1A1) products originates from two different dynamical pathways: a primary pathway (69%) evolving through one CoIn region to products and a smaller component (20%) sampling both CoIn regions enroute to products. Those that access both CoIn regions likely give rise to the more highly internally excited H2CO (X 1A1) products. The remaining trajectories (11%) dissociate to O (3P) + H2COmore »
- Authors:
-
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Univ. of Louisiana, Lafayette, LA (United States)
- Publication Date:
- Research Org.:
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1865331
- Grant/Contract Number:
- FG02-87ER13792; DGE-1845298; CHE-2003422
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 125; Journal Issue: 30; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Computational chemistry; Dissociation; Photodissociation; Bond cleavage; Energy
Citation Formats
Esposito, Vincent J., Liu, Tianlin, Wang, Guanghan, Caracciolo, Adriana, Vansco, Michael F., Marchetti, Barbara, Karsili, Tolga N. V., and Lester, Marsha I. Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory. United States: N. p., 2021.
Web. doi:10.1021/acs.jpca.1c03643.
Esposito, Vincent J., Liu, Tianlin, Wang, Guanghan, Caracciolo, Adriana, Vansco, Michael F., Marchetti, Barbara, Karsili, Tolga N. V., & Lester, Marsha I. Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory. United States. https://doi.org/10.1021/acs.jpca.1c03643
Esposito, Vincent J., Liu, Tianlin, Wang, Guanghan, Caracciolo, Adriana, Vansco, Michael F., Marchetti, Barbara, Karsili, Tolga N. V., and Lester, Marsha I. Tue .
"Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory". United States. https://doi.org/10.1021/acs.jpca.1c03643. https://www.osti.gov/servlets/purl/1865331.
@article{osti_1865331,
title = {Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory},
author = {Esposito, Vincent J. and Liu, Tianlin and Wang, Guanghan and Caracciolo, Adriana and Vansco, Michael F. and Marchetti, Barbara and Karsili, Tolga N. V. and Lester, Marsha I.},
abstractNote = {UV excitation of the CH2OO Criegee intermediate across most of the broad span of the (B 1A') – (X 1A') spectrum results in prompt dissociation to two energetically accessible asymptotes: O (1D) + H2CO (X 1A1) and O (3P) + H2CO (a 3A"). Dissociation proceeds on multiple singlet potential energy surfaces that are coupled by two regions of conical intersection (CoIn). Velocity map imaging (VMI) studies reveal a bimodal total kinetic energy (TKER) distribution for the O (1D) + H2CO (X 1A1) products with the major and minor components accounting for ca. 40% and ca. 20% on average of the available energy (Eavl), respectively. The unexpected low TKER component corresponds to highly internally excited H2CO (X 1A1) products accommodating ca. 80% of Eavl. Full dimensional trajectory calculations suggest that the bimodal TKER distribution of the O (1D) + H2CO (X 1A1) products originates from two different dynamical pathways: a primary pathway (69%) evolving through one CoIn region to products and a smaller component (20%) sampling both CoIn regions enroute to products. Those that access both CoIn regions likely give rise to the more highly internally excited H2CO (X 1A1) products. The remaining trajectories (11%) dissociate to O (3P) + H2CO (a 3A") products after traversing through both CoIn regions. Here, the complementary experimental and theoretical investigation provides insight on the photodissociation of CH2OO via multiple dissociation pathways through two regions of CoIn that control the branching and energy distributions of products.},
doi = {10.1021/acs.jpca.1c03643},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 30,
volume = 125,
place = {United States},
year = {Tue Jul 27 00:00:00 EDT 2021},
month = {Tue Jul 27 00:00:00 EDT 2021}
}
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