Photofragmentation of cyclobutanone at 200 nm: TD-DFT vs CASSCF electron diffraction
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arXiv
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| Autores principales: | , , , |
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| Formato: | Preprint |
| Publicado: |
2024
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| _version_ | 1866909180959391744 |
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| author | Daría, Alberto Martín Santa Hernández-Rodríguez, Javier Ibele, Lea M. Gómez, Sandra |
| author_facet | Daría, Alberto Martín Santa Hernández-Rodríguez, Javier Ibele, Lea M. Gómez, Sandra |
| contents | To simulate a 200 nm photoexcitation in cyclobutanone to the n-3s Rydberg state, classical trajectories were excited from a Wigner distribution to the singlet state manifold based on excitation energies and oscillator strenghts. Twelve singlet and twelve triplet states are treated using TD-B3LYP-D3/6-31+G$^{**}$ for the electronic structure and the nuclei are propagated with the Tully Surface Hopping method. Using TD-DFT, we are able to predict the bond cleavage that takes place on the S$_1$ surface as well as the ultrafast deactivation from the Rydberg n-3s state to the n$π^*$. After showing that triplet states and higher-lying singlet states do not play any crucial role during the early dynamics (i.e., the first 300 fs), the SA(6)-CASSCF(8,11)/aug-cc-pvDZ method is used as an electronic structure and the outcome of the non-adiabatic dynamic simulations is recomputed. Gas-phase ultrafast electron diffraction (GUED) spectra are computed for both electronic structure methods, showing significantly different results. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2401_07597 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Photofragmentation of cyclobutanone at 200 nm: TD-DFT vs CASSCF electron diffraction Daría, Alberto Martín Santa Hernández-Rodríguez, Javier Ibele, Lea M. Gómez, Sandra Chemical Physics To simulate a 200 nm photoexcitation in cyclobutanone to the n-3s Rydberg state, classical trajectories were excited from a Wigner distribution to the singlet state manifold based on excitation energies and oscillator strenghts. Twelve singlet and twelve triplet states are treated using TD-B3LYP-D3/6-31+G$^{**}$ for the electronic structure and the nuclei are propagated with the Tully Surface Hopping method. Using TD-DFT, we are able to predict the bond cleavage that takes place on the S$_1$ surface as well as the ultrafast deactivation from the Rydberg n-3s state to the n$π^*$. After showing that triplet states and higher-lying singlet states do not play any crucial role during the early dynamics (i.e., the first 300 fs), the SA(6)-CASSCF(8,11)/aug-cc-pvDZ method is used as an electronic structure and the outcome of the non-adiabatic dynamic simulations is recomputed. Gas-phase ultrafast electron diffraction (GUED) spectra are computed for both electronic structure methods, showing significantly different results. |
| title | Photofragmentation of cyclobutanone at 200 nm: TD-DFT vs CASSCF electron diffraction |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2401.07597 |