التفاصيل البيبلوغرافية
| العنوان: |
Impact of the Dynamic Electron Correlation on the Unusually Long Excited-State Lifetime of Thymine |
| المؤلفون: |
Woojin Park (2138110), Seunghoon Lee (201604), Miquel Huix-Rotllant (1299945), Michael Filatov (1299942), Cheol Ho Choi (1235448) |
| سنة النشر: |
2021 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Molecular Biology, Developmental Biology, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, 6.1, Thymine Non-radiative relaxation, mixed-reference spin-flip time-depe., thymine, Dynamic Electron Correlation, MRSF-TDDFT, bond length alternation distortion, NAMD, lifetime, Unusually Long Excited-State Lifetime, conversion, mechanism, S 1, S 2, model |
| الوصف: |
Non-radiative relaxation of the photoexcited thymine in the gas phase shows an unusually long excited-state lifetime, and, over the years, a number of models, i.e., S 1 -trapping, S 2 -trapping, and S 1 &S 2 -trapping, have been put forward to explain its mechanism. Here, we investigate this mechanism using non-adiabatic molecular dynamics (NAMD) simulations in connection with the recently developed mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT) method. We show that the previously predicted S 2 -trapping model was due to an artifact caused by an insufficient account of the dynamic electron correlation. The current work supports the S 1 -trapping mechanism with two lifetimes, τ 1 = 30 ± 1 fs and τ 2 = 6.1 ± 0.035 ps, quantitatively consistent with the recent time-resolved experiments. Upon excitation to the S 2 (ππ*) state, thymine undergoes an ultrafast (ca. 30 fs) S 2 →S 1 internal conversion and resides around the minimum on the S 1 (n O π*) surface, slowly decaying to the ground state (ca. 6.1 ps). While the S 2 →S 1 internal conversion is mediated by fast bond length alternation distortion, the subsequent S 1 →S 0 occurs through several conical intersections, involving a slow puckering motion. |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/Impact_of_the_Dynamic_Electron_Correlation_on_the_Unusually_Long_Excited-State_Lifetime_of_Thymine/14522561 |
| DOI: |
10.1021/acs.jpclett.1c00712.s001 |
| الاتاحة: |
https://doi.org/10.1021/acs.jpclett.1c00712.s001 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.FFCDF9F6 |
| قاعدة البيانات: |
BASE |