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...
Autores principales: | , , , |
---|---|
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 |