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While the photophysics of closed-shell organic molecules is well established, much less is known about open-shell systems containing interacting radical pairs. In this work, we investigate the ultrafast excited state dynamics of a singlet verdazyl diradical system in solution using transient absorption (TA) spectroscopy for the first time. Following 510 nm excitation of the excitonic S0 → S1 transition, we detected TA signals in the 530–950 nm region from the S1 population that decayed exponentially within a few picoseconds to form a vibrationally hot S0* population via internal conversion. The dependence of the S1 decay rate on solvent and radical–radical distance revealed that the excited state possesses charge-transfer character and likely accesses the S0 state via torsional motion. The ultrafast internal conversion decay mechanism at play in our open-shell verdazyl diradicals is in stark contrast with other closed-shell, carbonyl-containing organic chromophores, which exhibit ultrafast intersystem crossing to produce long-lived triplet states as the major S1 decay pathway.
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How excitation wavelength affects excited state dynamics in o -nitrophenol: A theoretical perspective
The excited-state dynamics of o-nitrophenol have been explored using trajectory surface hopping nonadiabatic dynamics combined with floating occupation molecular orbital complete active space configuration interaction. We focus on the effect of excitation energy on the subsequent dynamics. The absorption spectrum of o-nitrophenol has two peaks, centered at 3.9 eV (∼320 nm) and 5.1 eV (∼240 nm), and we performed dynamics starting from each of these peaks. The results show that even though the relaxation time constants are similar for the two excitation windows, the underlying dynamics are different. When exciting to the low energy peak, the dynamics are dominated by intramolecular proton transfer followed by internal conversion to the ground state, while exciting to the high-energy peak leads to fast internal conversion to the first excited state and slower decay to the ground state. In this case, intramolecular proton transfer does not occur as frequently, and many trajectories decay to the ground state through conical intersections without proton transfer. By calculating spin–orbit coupling values along the trajectories, we also show that intersystem crossing is possible. Based on the Landau–Zener probability formula, we estimate that there is about a 30%–40% probability that intersystem crossing will occur within 1 ps.
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- PAR ID:
- 10645632
- Publisher / Repository:
- AIP
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 163
- Issue:
- 2
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1063/5.0274633
