Cargando…

Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A(2)Σ(+)) with CH(4), CH(3)OH, and CO(2)

[Image: see text] The electronic quenching of NO(A(2)Σ(+)) with molecular partners occurs through complex non-adiabatic dynamics that occurs on multiple coupled potential energy surfaces. Moreover, the propensity for NO(A(2)Σ(+)) electronic quenching depends heavily on the strength and nature of the...

Descripción completa

Detalles Bibliográficos
Autores principales: Bridgers, Aerial N., Urquilla, Justin A., Im, Julia, Petit, Andrew S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10476188/
https://www.ncbi.nlm.nih.gov/pubmed/37552562
http://dx.doi.org/10.1021/acs.jpca.3c03981
_version_ 1785100872655568896
author Bridgers, Aerial N.
Urquilla, Justin A.
Im, Julia
Petit, Andrew S.
author_facet Bridgers, Aerial N.
Urquilla, Justin A.
Im, Julia
Petit, Andrew S.
author_sort Bridgers, Aerial N.
collection PubMed
description [Image: see text] The electronic quenching of NO(A(2)Σ(+)) with molecular partners occurs through complex non-adiabatic dynamics that occurs on multiple coupled potential energy surfaces. Moreover, the propensity for NO(A(2)Σ(+)) electronic quenching depends heavily on the strength and nature of the intermolecular interactions between NO(A(2)Σ(+)) and the molecular partner. In this paper, we explore the electronic quenching mechanisms of three systems: NO(A(2)Σ(+)) + CH(4), NO(A(2)Σ(+)) + CH(3)OH, and NO(A(2)Σ(+)) + CO(2). Using EOM-EA-CCSD calculations, we rationalize the very low electronic quenching cross-section of NO(A(2)Σ(+)) + CH(4) as well as the outcomes observed in previous NO + CH(4) photodissociation studies. Our analysis of NO(A(2)Σ(+)) + CH(3)OH suggests that it will undergo facile electronic quenching mediated by reducing the intermolecular distance and significantly stretching the O–H bond of CH(3)OH. For NO(A(2)Σ(+)) + CO(2), intermolecular attractions lead to a series of low-energy ON–OCO conformations in which the CO(2) is significantly bent. For both the NO(A(2)Σ(+)) + CH(3)OH and NO(A(2)Σ(+)) + CO(2) systems, we see evidence of the harpoon mechanism and low-energy conical intersections between NO(A(2)Σ(+)) + M and NO(X(2)Π) + M. Overall, this work provides the first detailed theoretical study on the NO(A(2)Σ(+)) + M potential energy surface of each of these systems and will inform future velocity map imaging experiments.
format Online
Article
Text
id pubmed-10476188
institution National Center for Biotechnology Information
language English
publishDate 2023
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-104761882023-09-05 Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A(2)Σ(+)) with CH(4), CH(3)OH, and CO(2) Bridgers, Aerial N. Urquilla, Justin A. Im, Julia Petit, Andrew S. J Phys Chem A [Image: see text] The electronic quenching of NO(A(2)Σ(+)) with molecular partners occurs through complex non-adiabatic dynamics that occurs on multiple coupled potential energy surfaces. Moreover, the propensity for NO(A(2)Σ(+)) electronic quenching depends heavily on the strength and nature of the intermolecular interactions between NO(A(2)Σ(+)) and the molecular partner. In this paper, we explore the electronic quenching mechanisms of three systems: NO(A(2)Σ(+)) + CH(4), NO(A(2)Σ(+)) + CH(3)OH, and NO(A(2)Σ(+)) + CO(2). Using EOM-EA-CCSD calculations, we rationalize the very low electronic quenching cross-section of NO(A(2)Σ(+)) + CH(4) as well as the outcomes observed in previous NO + CH(4) photodissociation studies. Our analysis of NO(A(2)Σ(+)) + CH(3)OH suggests that it will undergo facile electronic quenching mediated by reducing the intermolecular distance and significantly stretching the O–H bond of CH(3)OH. For NO(A(2)Σ(+)) + CO(2), intermolecular attractions lead to a series of low-energy ON–OCO conformations in which the CO(2) is significantly bent. For both the NO(A(2)Σ(+)) + CH(3)OH and NO(A(2)Σ(+)) + CO(2) systems, we see evidence of the harpoon mechanism and low-energy conical intersections between NO(A(2)Σ(+)) + M and NO(X(2)Π) + M. Overall, this work provides the first detailed theoretical study on the NO(A(2)Σ(+)) + M potential energy surface of each of these systems and will inform future velocity map imaging experiments. American Chemical Society 2023-08-08 /pmc/articles/PMC10476188/ /pubmed/37552562 http://dx.doi.org/10.1021/acs.jpca.3c03981 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Bridgers, Aerial N.
Urquilla, Justin A.
Im, Julia
Petit, Andrew S.
Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A(2)Σ(+)) with CH(4), CH(3)OH, and CO(2)
title Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A(2)Σ(+)) with CH(4), CH(3)OH, and CO(2)
title_full Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A(2)Σ(+)) with CH(4), CH(3)OH, and CO(2)
title_fullStr Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A(2)Σ(+)) with CH(4), CH(3)OH, and CO(2)
title_full_unstemmed Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A(2)Σ(+)) with CH(4), CH(3)OH, and CO(2)
title_short Theoretical Study of the Photochemical Mechanisms of the Electronic Quenching of NO(A(2)Σ(+)) with CH(4), CH(3)OH, and CO(2)
title_sort theoretical study of the photochemical mechanisms of the electronic quenching of no(a(2)σ(+)) with ch(4), ch(3)oh, and co(2)
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10476188/
https://www.ncbi.nlm.nih.gov/pubmed/37552562
http://dx.doi.org/10.1021/acs.jpca.3c03981
work_keys_str_mv AT bridgersaerialn theoreticalstudyofthephotochemicalmechanismsoftheelectronicquenchingofnoa2swithch4ch3ohandco2
AT urquillajustina theoreticalstudyofthephotochemicalmechanismsoftheelectronicquenchingofnoa2swithch4ch3ohandco2
AT imjulia theoreticalstudyofthephotochemicalmechanismsoftheelectronicquenchingofnoa2swithch4ch3ohandco2
AT petitandrews theoreticalstudyofthephotochemicalmechanismsoftheelectronicquenchingofnoa2swithch4ch3ohandco2