Ultrafast Photochemistry and Electron Diffraction for Cyclobutanone in the S2 State: Surface Hopping with Time-Dependent Density Functional Theory
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arXiv
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| Autori principali: | , , , , |
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| Natura: | Preprint |
| Pubblicazione: |
2024
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| _version_ | 1866910537447636992 |
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| author | Miller, Ericka Roy Hoehn, Sean J. Kumar, Abhijith Jiang, Dehua Parker, Shane M. |
| author_facet | Miller, Ericka Roy Hoehn, Sean J. Kumar, Abhijith Jiang, Dehua Parker, Shane M. |
| contents | We simulate the photodynamics of gas-phase cyclobutanone excited to the S$_2$ state using fewest switches surface hopping (FSSH) dynamics powered by time-dependent density functional theory (TDDFT). We predict a total C3+C2 photoproduct yield of 9%, with a C3:C2 product ratio of 1:8. Two primary S$_2$$\rightarrow$S$_1$ conical intersections are identified: $β$ stretch and CCH bend, with the higher energy $β$ stretch being associated with sub-picosecond S$_2$ decay. Excited state lifetimes computed with respect to electronic state populations were found to be 7.0 ps (S$_2$$\rightarrow$S$_1$) and 550 fs (S$_1$$\rightarrow$S$_0$). We also generate time-resolved difference pair distribution functions ($Δ$PDFs) from our TDDFT-FSSH dynamics results in order to generate direct comparisons to ultrafast electron diffraction experiment observables. Global and target analysis of time-resolved $Δ$PDFs produced a distinct set of lifetimes: i) a 0.462 ps decay, and ii) a 16.8 ps decay that both resemble the S$_2$ minimum, as well as iii) a long ($>$ nanosecond) decay that resembles the S$_1$ minimum geometry and the fully separated C3/C2 products. Finally, we contextualize our results by considering the impact of the most likely sources of significant errors. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2402_10336 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Ultrafast Photochemistry and Electron Diffraction for Cyclobutanone in the S2 State: Surface Hopping with Time-Dependent Density Functional Theory Miller, Ericka Roy Hoehn, Sean J. Kumar, Abhijith Jiang, Dehua Parker, Shane M. Chemical Physics We simulate the photodynamics of gas-phase cyclobutanone excited to the S$_2$ state using fewest switches surface hopping (FSSH) dynamics powered by time-dependent density functional theory (TDDFT). We predict a total C3+C2 photoproduct yield of 9%, with a C3:C2 product ratio of 1:8. Two primary S$_2$$\rightarrow$S$_1$ conical intersections are identified: $β$ stretch and CCH bend, with the higher energy $β$ stretch being associated with sub-picosecond S$_2$ decay. Excited state lifetimes computed with respect to electronic state populations were found to be 7.0 ps (S$_2$$\rightarrow$S$_1$) and 550 fs (S$_1$$\rightarrow$S$_0$). We also generate time-resolved difference pair distribution functions ($Δ$PDFs) from our TDDFT-FSSH dynamics results in order to generate direct comparisons to ultrafast electron diffraction experiment observables. Global and target analysis of time-resolved $Δ$PDFs produced a distinct set of lifetimes: i) a 0.462 ps decay, and ii) a 16.8 ps decay that both resemble the S$_2$ minimum, as well as iii) a long ($>$ nanosecond) decay that resembles the S$_1$ minimum geometry and the fully separated C3/C2 products. Finally, we contextualize our results by considering the impact of the most likely sources of significant errors. |
| title | Ultrafast Photochemistry and Electron Diffraction for Cyclobutanone in the S2 State: Surface Hopping with Time-Dependent Density Functional Theory |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2402.10336 |