| _version_ | 1866902045400760320 |
|---|---|
| author | Bridgers-Anguiano, Aerial |
| author_facet | Bridgers-Anguiano, Aerial |
| contents | <p>The electronic quenching of NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>) with molecular partners occurs through complex non-adiabatic dynamics that occurs on multiple coupled potential energy surfaces. Moreover, the propensity for NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>) electronic quenching depends heavily on the strength and nature of the intermolecular interactions between NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>) and the molecular partner. In this thesis, we explore the electronic quenching mechanisms of four systems: NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>4</sub>, NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>3</sub>OH, NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CO<sub>2</sub>, and NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+C<sub>2</sub>H<sub>2</sub>. Using EOM-EA-CCSD calculations, we rationalize the very low electronic quenching cross-section of NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>4 </sub>as well as the outcomes observed in previous NO+CH<sub>4</sub>photodissociation studies. Our analysis of NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>3</sub>OH suggests that it will undergo facile electronic quenching mediated by reducing the intermolecular distance and significantly stretching the O-H bond of CH<sub>3</sub>OH. For NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CO<sub>2 </sub>and NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+C<sub>2</sub>H<sub>2</sub>, intermolecular attractions lead to a series of low-energy ON-OCO or ON-C<sub>2</sub>H<sub>2</sub>conformations in which the CO<sub>2</sub> or the C<sub>2</sub>H<sub>2</sub> is significantly bent. For the NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>3</sub>OH, NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CO<sub>2</sub>, and NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+C<sub>2</sub>H<sub>2 </sub>systems, we see evidence of the harpoon mechanism and low-energy conical intersections between NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+M and NO (<em>X</em><sup>2</sup>Π)+M. Overall, this work provides the first detailed theoretical study on the NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+M potential energy surface of each of these systems.</p> |
| format | Recurso digital |
| id | zenodo_https___doi_org_10_5281_zenodo_12748407 |
| institution | Zenodo |
| language | eng |
| publishDate | 2024 |
| publisher | Zenodo |
| record_format | zenodo |
| spellingShingle | EXPLORING THE MECHANISM OF THE ELECTRONIC QUENCHING OF NO(A2Σ+) WITH CH4, CH3OH, CO2, AND C2H2 Bridgers-Anguiano, Aerial NO(A2Σ+) photochemistry excited states electronic quenching conical intersection harpoon mechanism <p>The electronic quenching of NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>) with molecular partners occurs through complex non-adiabatic dynamics that occurs on multiple coupled potential energy surfaces. Moreover, the propensity for NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>) electronic quenching depends heavily on the strength and nature of the intermolecular interactions between NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>) and the molecular partner. In this thesis, we explore the electronic quenching mechanisms of four systems: NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>4</sub>, NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>3</sub>OH, NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CO<sub>2</sub>, and NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+C<sub>2</sub>H<sub>2</sub>. Using EOM-EA-CCSD calculations, we rationalize the very low electronic quenching cross-section of NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>4 </sub>as well as the outcomes observed in previous NO+CH<sub>4</sub>photodissociation studies. Our analysis of NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>3</sub>OH suggests that it will undergo facile electronic quenching mediated by reducing the intermolecular distance and significantly stretching the O-H bond of CH<sub>3</sub>OH. For NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CO<sub>2 </sub>and NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+C<sub>2</sub>H<sub>2</sub>, intermolecular attractions lead to a series of low-energy ON-OCO or ON-C<sub>2</sub>H<sub>2</sub>conformations in which the CO<sub>2</sub> or the C<sub>2</sub>H<sub>2</sub> is significantly bent. For the NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CH<sub>3</sub>OH, NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+CO<sub>2</sub>, and NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+C<sub>2</sub>H<sub>2 </sub>systems, we see evidence of the harpoon mechanism and low-energy conical intersections between NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+M and NO (<em>X</em><sup>2</sup>Π)+M. Overall, this work provides the first detailed theoretical study on the NO (<em>A</em><sup>2</sup>Σ<sup>+</sup>)+M potential energy surface of each of these systems.</p> |
| title | EXPLORING THE MECHANISM OF THE ELECTRONIC QUENCHING OF NO(A2Σ+) WITH CH4, CH3OH, CO2, AND C2H2 |
| topic | NO(A2Σ+) photochemistry excited states electronic quenching conical intersection harpoon mechanism |
| url | https://doi.org/10.5281/zenodo.12748407 |