Dynamics of Isolated 1,8-Naphthalimide and N-Methyl-1,8-naphthalimide: An Experimental and Computational Study

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• 作者：Thiemo Gerbich ; Hans-Christian Schmitt ; Ingo Fischer ; Roland Mitrić ; Jens Petersen
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：April 7, 2016
• 年：2016
• 卷：120
• 期：13
• 页码：2089-2095
• 全文大小：385K
• ISSN：1520-5215

文摘

In this work we investigate the excited-state structure and dynamics of the two molecules 1,8-naphthalimide (NI) and N-methyl-1,8-naphthalimide (Me-NI) in the gas phase by picosecond time- and frequency-resolved multiphoton ionization spectroscopy. The energies of several electronically excited singlet and triplet states and the S₁ vibrational wavenumbers were calculated. Nonadiabatic dynamics simulations support the analysis of the radiationless deactivation processes. The origin of the S₁ ← S₀ (ππ*) transition was found at 30 082 cm^–1 for NI and at 29 920 cm^–1 for Me-NI. Furthermore, a couple of low-lying vibrational bands were resolved in the spectra of both molecules. In the time-resolved scans a biexponential decay was apparent for both Me-NI and NI. The fast time constant is in the range of 10–20 ps, whereas the second one is in the nanosecond range. In accordance with the dynamics simulations, intersystem crossing to the fourth triplet state S₁ (ππ*) → T₄ (nπ*) is the main deactivation process for Me-NI due to a large spin–orbit coupling between these states. Only for significant vibrational excitation internal conversion via a conical intersection becomes a relevant deactivation pathway.