End-to-End Photodissociation Dynamics of Energized H$_2$COO
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arXiv
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| Autores principales: | , , , |
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| Formato: | Preprint |
| Publicado: |
2025
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| _version_ | 1866909705150922752 |
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| author | Yin, Cangtao Käser, Silvan Upadhyay, Meenu Meuwly, Markus |
| author_facet | Yin, Cangtao Käser, Silvan Upadhyay, Meenu Meuwly, Markus |
| contents | The end-to-end dynamics of the smallest energized Criegee intermediate, H$_2$COO, was characterized for vibrational excitation close to and a few kcal/mol above the barrier for hydrogen transfer. From an aggregate of at least 5 $μ$s of molecular dynamics simulations using a neural network-representation of CASPT2/aug-cc-pVTZ reference data, the branching ratios into molecular products HCO+OH, CO$_2$+H$_2$, or H$_2$O+CO was quantitatively determined. Consistent with earlier calculations and recent experiments, decay into HCO+OH was found to be rare $(\sim 2 \%)$ whereas the other two molecular product channels are accessed with fractions of $\sim 30 \%$ and $\sim 20 \%$, respectively. On the 1 ns time scale, which was the length of an individual MD simulation, more than 40 \% of the systems remain in the reactant state due to partial intramolecular vibrational redistribution (IVR). Formation of CO$_2$+H$_2$ occurs through a bifurcating pathway, one of which passes through formic acid whereas the more probable route connects the di-radical OCH$_2$O with the product through a low-lying transition state. Notably, none of the intermediates along the pathway accumulate and their maximum concentration always remains well below 5 \%. This work demonstrates that atomistic simulations with global reactive machine-learned energy functions provide a quantitative understanding of the chemistry and reaction dynamics for atmospheric reactions in the gas phase. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2507_18964 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | End-to-End Photodissociation Dynamics of Energized H$_2$COO Yin, Cangtao Käser, Silvan Upadhyay, Meenu Meuwly, Markus Chemical Physics The end-to-end dynamics of the smallest energized Criegee intermediate, H$_2$COO, was characterized for vibrational excitation close to and a few kcal/mol above the barrier for hydrogen transfer. From an aggregate of at least 5 $μ$s of molecular dynamics simulations using a neural network-representation of CASPT2/aug-cc-pVTZ reference data, the branching ratios into molecular products HCO+OH, CO$_2$+H$_2$, or H$_2$O+CO was quantitatively determined. Consistent with earlier calculations and recent experiments, decay into HCO+OH was found to be rare $(\sim 2 \%)$ whereas the other two molecular product channels are accessed with fractions of $\sim 30 \%$ and $\sim 20 \%$, respectively. On the 1 ns time scale, which was the length of an individual MD simulation, more than 40 \% of the systems remain in the reactant state due to partial intramolecular vibrational redistribution (IVR). Formation of CO$_2$+H$_2$ occurs through a bifurcating pathway, one of which passes through formic acid whereas the more probable route connects the di-radical OCH$_2$O with the product through a low-lying transition state. Notably, none of the intermediates along the pathway accumulate and their maximum concentration always remains well below 5 \%. This work demonstrates that atomistic simulations with global reactive machine-learned energy functions provide a quantitative understanding of the chemistry and reaction dynamics for atmospheric reactions in the gas phase. |
| title | End-to-End Photodissociation Dynamics of Energized H$_2$COO |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2507.18964 |